Accessing Five- and Seven-Membered Phosphorus-Based Heterocycles via Cycloaddition Reactions of Azophosphines

Heterocycles containing both phosphorus and nitrogen have seen increasing use in recent years in luminescent materials, coordination chemistry and building blocks for inorganic polymers, yet their chemistry is currently dominated by five- and six-memberd derivatives. Seven-membered P/N heterocycles are comparatively scarce and lack general, high yielding syntheses. We explore the synthesis and characterisation of 1,2,5-diazaphosphepines from azophosphines. The mechanism has been probed in detail with both computational and experimental studies supporting a stepwise mechanism to form a five-membered ring, and subsequent ring expansion to the diazaphosphepine. Regioselective synthesis of five- and seven-membered rings is possible using asymmetric alkynes. The Lewis acidic borane B(C6F5)3 could either catalyse the formation of the seven-membered ring (iPr derivative) or trap out a key intermediate via a frustrated Lewis pair (FLP) mechanism (tBu derivative)

Accessing five- and seven-membered phosphorus-based heterocycles via cycloaddition reactions of azophosphines

Heterocycles containing both phosphorus and nitrogen have seen increasing use in recent years in luminescent materials, coordination chemistry and as building blocks for inorganic polymers, yet their chemistry is currently dominated by five- and six-membered derivatives. Seven-membered P/N heterocycles are comparatively scarce and lack general, high yielding syntheses. Here, we explore the synthesis and characterisation of 1,2,5-diazaphosphepines from azophosphines. The mechanism has been probed in detail with both computational and experimental studies supporting a stepwise mechanism to form a five-membered ring, and subsequent ring expansion to the diazaphosphepine. Regioselective synthesis of five- and seven-membered rings is possible using asymmetric alkynes. The Lewis acidic borane B(C6F5)3 could either catalyse the formation of the seven-membered ring (iPr derivative) or trap out a key intermediate via a frustrated Lewis pair (FLP) mechanism (tBu derivative)

Azophosphines:Synthesis, Structure and Coordination Chemistry

The conceptual replacement of nitrogen with phosphorus in common organic functional groups unlocks new properties and reactivity. The phosphorus-containing analogues of triazenes are underexplored but offer great potential as flexible and small bite-angle ligands. This manuscript explores the synthesis and characterisation of a family of air-stable azophosphine-borane complexes, and their subsequent deprotection to the free azophosphines. These compounds are structurally characterised, both experimentally and computationally, and highlight the availability of the phosphorus lone pair for coordination. This is confirmed by demonstrating that neutral azophosphines can act as ligands in Ru complexes, and can coordinate as monodentate or bidentate ligands in a controlled manner, in contrast to their nitrogen analogues

(How Much) Does a Private WAN Improve Cloud Performance?

The buildout of private Wide Area Networks (WANs) by cloud providers allows providers to extend their network to more locations and establish direct connectivity with end user Internet Service Providers (ISPs). Tenants of the cloud providers benefit from this proximity to users, which is supposed to provide improved performance by bypassing the public Internet. However, the performance impact of private WANs is not widely understood. To isolate the impact of a private WAN, we measure from globally distributed vantage points to a large cloud provider, comparing performance when using its worldwide WAN and when forcing traffic to instead use the public Internet. The benefits are not universal. While 40% of our vantage points saw improved performance when using the WAN, half of our vantage points did not see significant performance improvement, and 10% had better performance over the public Internet. We find that the benefits of the private WAN tend to improve with client-to-server distance, but that the benefits (or drawbacks) to a particular vantage point depend on specifics of its geographic and network connectivity

Azophosphines:Synthesis, Structure and Coordination Chemistry

The conceptual replacement of nitrogen with phosphorus in common organic functional groups unlocks new properties and reactivity. The phosphorus-containing analogues of triazenes are underexplored but offer great potential as flexible and small bite-angle ligands. This manuscript explores the synthesis and characterisation of a family of air-stable azophosphine-borane complexes, and their subsequent deprotection to the free azophosphines. These compounds are structurally characterised, both experimentally and computationally, and highlight the availability of the phosphorus lone pair for coordination. This is confirmed by demonstrating that neutral azophosphines can act as ligands in Ru complexes, and can coordinate as monodentate or bidentate ligands in a controlled manner, in contrast to their nitrogen analogues.</p

Azophosphines:Synthesis, Structure and Coordination Chemistry

The conceptual replacement of nitrogen with phosphorus in common organic functional groups unlocks new properties and reactivity. The phosphorus-containing analogues of triazenes are underexplored but offer great potential as flexible and small bite-angle ligands. This manuscript explores the synthesis and characterisation of a family of air-stable azophosphine-borane complexes, and their subsequent deprotection to the free azophosphines. These compounds are structurally characterised, both experimentally and computationally, and highlight the availability of the phosphorus lone pair for coordination. This is confirmed by demonstrating that neutral azophosphines can act as ligands in Ru complexes, and can coordinate as monodentate or bidentate ligands in a controlled manner, in contrast to their nitrogen analogues.</p

Sibyl:A Practical Internet Route Oracle

Network operators measure Internet routes to troubleshoot problems, and researchers measure routes to characterize the Internet. However, they still rely on decades-old tools like traceroute, BGP route collectors, and Looking Glasses, all of which permit only a single query about Internet routes—what is the path from here to there? This limited interface complicates answering queries about routes such as "find routes traversing the Level3/AT&T peering in Atlanta," to understand the scope of a reported problem there. This paper presents Sibyl, a system that takes rich queries that researchers and operators express as regular expressions, then issues and returns traceroutes that match even if it has never measured a matching path in the past. Sibyl achieves this goal in three steps. First, to maximize its coverage of Internet routing, Sibyl integrates together diverse sets of traceroute vantage points that provide complementary views, measuring from thousands of networks in total. Second, because users may not know which measurements will traverse paths of interest, and because vantage point resource constraints keep Sibyl from tracing to all destinations from all sources, Sibyl uses historical measurements to predict which new ones are likely to match a query. Finally, based on these predictions, Sibyl optimizes across concurrent queries to decide which measurements to issue given resource constraints. We show that Sibyl provides researchers and operators with the routing information they need—in fact, it matches 76% of the queries that it could match if an oracle told it which measurements to issue

Poorer White Matter Microstructure Predicts Slower and More Variable Reaction Time Performance: Evidence for a Neural Noise Hypothesis in a Large Lifespan Cohort

Most prior research has focused on characterizing averages in cognition, brain characteristics, or behavior, and attempting to predict differences in these averages among individuals. However, this overwhelming focus on mean levels may leave us with an incomplete picture of what drives individual differences in behavioral phenotypes by ignoring the variability of behavior around an individual's mean. In particular, enhanced white matter (WM) structural microstructure has been hypothesized to support consistent behavioral performance by decreasing Gaussian noise in signal transfer. Conversely, lower indices of WM microstructure are associated with greater within-subject variance in the ability to deploy performance-related resources, especially in clinical populations. We tested a mechanistic account of the “neural noise” hypothesis in a large adult lifespan cohort (Cambridge Centre for Ageing and Neuroscience) with over 2500 adults (ages 18-102; 1508 female; 1173 male; 2681 behavioral sessions; 708 MRI scans) using WM fractional anisotropy to predict mean levels and variability in reaction time performance on a simple behavioral task using a dynamic structural equation model. By modeling robust and reliable individual differences in within-person variability, we found support for a neural noise hypothesis (Kail, 1997), with lower fractional anisotropy predicted individual differences in separable components of behavioral performance estimated using dynamic structural equation model, including slower mean responses and increased variability. These effects remained when including age, suggesting consistent effects of WM microstructure across the adult lifespan unique from concurrent effects of aging. Crucially, we show that variability can be reliably separated from mean performance using advanced modeling tools, enabling tests of distinct hypotheses for each component of performance

Distinct components of cardiovascular health are linked with age-related differences in cognitive abilities

Cardiovascular ageing contributes to cognitive impairment. However, the unique and synergistic contributions of multiple cardiovascular factors to cognitive function remain unclear because they are often condensed into a single composite score or examined in isolation. We hypothesized that vascular risk factors, electrocardiographic features and blood pressure indices reveal multiple latent vascular factors, with independent contributions to cognition. In a population-based deep-phenotyping study (n = 708, age 18–88), path analysis revealed three latent vascular factors dissociating the autonomic nervous system response from two components of blood pressure. These three factors made unique and additive contributions to the variability in crystallized and fluid intelligence. The discrepancy in fluid relative to crystallized intelligence, indicative of cognitive decline, was associated with a latent vascular factor predominantly expressing pulse pressure. This suggests that higher pulse pressure is associated with cognitive decline from expected performance. The effect was stronger in older adults. Controlling pulse pressure may help to preserve cognition, particularly in older adults. Our findings highlight the need to better understand the multifactorial nature of vascular aging