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Paleoclimate reconstructions are now integral to climate assessments, yet the consequences of using different methodologies and proxy data require rigorous benchmarking. Pseudoproxy experiments (PPEs) provide a tractable and transparent test bed for evaluating climate reconstruction methods and their sensitivity to aspects of real-world proxy networks. Here we develop a dataset that leverages proxy system models (PSMs) for this purpose, which emulates the essential physical, chemical, biological, and geological processes that translate climate signals into proxy records, making these synthetic proxies more relevant to the real world. We apply a suite of PSMs to emulate the widely-used PAGES 2k dataset, including realistic spatiotemporal sampling and error structure. A hierarchical approach allows us to produce many variants of this base dataset, isolating the impact of sampling bias in time and space, representation error, sampling error, and other assumptions. Combining these various experiments produces a rich dataset (“pseudoPAGES2k”) for many applications. As an illustration, we show how to conduct a PPE with this dataset based on emerging climate field reconstruction techniques.

 

Externally heated diamond anvil cells provide a stable and uniform thermal environment, making them a versatile device to simultaneously generate high-pressure and high-temperature conditions in various fields of research, such as condensed matter physics, materials science, chemistry, and geosciences. The present study features the Externally Heated Diamond ANvil Cell Experimentation (EH-DANCE) system, a versatile configuration consisting of a diamond anvil cell with a customized microheater for stable resistive heating, bidirectional pressure control facilitated by compression and decompression membranes, and a water-cooled enclosure suitable for vacuum and controlled atmospheres. This integrated system excels with its precise control of both pressure and temperature for mineral and materials science research under extreme conditions. We showcase the capabilities of the system through its successful application in the investigation of the melting temperature and thermal equation of state of high-pressure ice-VII at temperatures up to 1400 K. The system was also used to measure the elastic properties of solid ice-VII and liquid H2O using Brillouin scattering and Raman spectra of carbonates using Raman spectroscopy, highlighting the potential of the EH-DANCE system in high-pressure research.

 

Abstract We use theNorthern Hemisphere Tree-RingNetwork Development (NTREND) tree-ring database to examine the effects of using a small, highly-sensitive proxy network for paleotemperature data assimilation over the last millennium. We first evaluate our methods using pseudo-proxy experiments. These indicate that spatial assimilations using this network are skillful in the extratropical Northern Hemisphere and improve on previous NTREND reconstructions based on Point-by-Point regression. We also find our method is sensitive to climate model biases when the number of sites becomes small. Based on these experiments, we then assimilate the real NTREND network. To quantify model prior uncertainty, we produce 10 separate reconstructions, each assimilating a different climate model. These reconstructions are most dissimilar prior to 1100 CE, when the network becomes sparse, but show greater consistency as the network grows. Temporal variability is also underestimated before 1100 CE. Our assimilation method produces spatial uncertainty estimates and these identify treeline North America and eastern Siberia as regions that would most benefit from development of new millennial-length temperature-sensitive tree-ring records. We compare our multi-model mean reconstruction to five existing paleo-temperature products to examine the range of reconstructed responses to radiative forcing. We find substantial differences in the spatial patterns and magnitudes of reconstructed responses to volcanic eruptions and in the transition between the Medieval epoch and Little Ice Age. These extant uncertainties call for the development of a paleoclimate reconstruction intercomparison framework for systematically examining the consequences of proxy network composition and reconstruction methodology and for continued expansion of tree-ring proxy networks. 

The Stille cross‐coupling reaction is one of the most common strategies for the construction of C−C bonds. Despite notable strides in the advancement of the Stille reaction, persistent challenges persist in hindering its greener evolution. These challenges encompass multiple facets, such as the high cost of precious metals and ligands, the demand for various additives, and the slow reaction rate. In comparison to the dominant palladium‐catalysed Stille reactions, cost‐effective nickel‐catalysed systems lag behind, and enantioconvergent Stille reactions of racemic stannanes remain undeveloped. Herein, we present a pioneering instance of nickel‐catalysed enantioconvergent Stille cross‐coupling reactions of racemic stannane reagents, resulting in the formation of C−C bonds in good to high yields with excellent stereoselectivity. This strategy provides a practical, scalable, and operationally straightforward method for the synthesis of C(sp³)−C(sp³), C(sp³)−C(sp²), and C(sp³)−C(sp) bonds under exceptionally mild conditions (without additives and bases, ambient temperature). The innovative use of synergistic photoredox/nickel catalysis enables a novel single‐electron transmetalation process of stannane reagents, providing a new research paradigm of Stille reactions.

 

The Stille cross‐coupling reaction is one of the most common strategies for the construction of C−C bonds. Despite notable strides in the advancement of the Stille reaction, persistent challenges persist in hindering its greener evolution. These challenges encompass multiple facets, such as the high cost of precious metals and ligands, the demand for various additives, and the slow reaction rate. In comparison to the dominant palladium‐catalysed Stille reactions, cost‐effective nickel‐catalysed systems lag behind, and enantioconvergent Stille reactions of racemic stannanes remain undeveloped. Herein, we present a pioneering instance of nickel‐catalysed enantioconvergent Stille cross‐coupling reactions of racemic stannane reagents, resulting in the formation of C−C bonds in good to high yields with excellent stereoselectivity. This strategy provides a practical, scalable, and operationally straightforward method for the synthesis of C(sp³)−C(sp³), C(sp³)−C(sp²), and C(sp³)−C(sp) bonds under exceptionally mild conditions (without additives and bases, ambient temperature). The innovative use of synergistic photoredox/nickel catalysis enables a novel single‐electron transmetalation process of stannane reagents, providing a new research paradigm of Stille reactions.