Publications

Supramolecular hosts offer defined microenvironments that facilitate selective host-guest interactions, enabling reactivity that would otherwise be challenging in bulk solution. While impressive rate enhancements and selectivities have been reported, similar reactivity can often be accessed through modifications of reaction conditions even in the absence of the host. We report here an oxidative addition of aryl halides across the metal centers in Cu(I) and Pd(II) organometallics that is assisted by the presence of a supramolecular host, realized via electrostatic stabilization and increased local substrate concentrations. When reaction conditions were screened to assess background reactivity, alternative reactivity (typically decomposition) resulted, indicating that encapsulation led to host-selective reaction trajectories.

Abstract Study Objectives Healthy sleep is important for adolescent neurodevelopment, and relationships between brain structure and sleep can vary in strength over this maturational window. Although cortical gyrification is increasingly considered a useful index for understanding cognitive and emotional outcomes in adolescence, and sleep is also a strong predictor of such outcomes, we know relatively little about associations between cortical gyrification and sleep. We aimed to identify developmentally invariant (stable across age) or developmentally specific (observed only during discrete age intervals) gyrification-sleep relationships in young people. Methods A total of 252 Neuroimaging and Pediatric Sleep Databank participants (9–26 years; 58.3% female) completed wrist actigraphy and a structural MRI scan. Local gyrification index (lGI) was estimated for 34 bilateral brain regions. Naturalistic sleep characteristics (duration, timing, continuity, and regularity) were estimated from wrist actigraphy. Regularized regression for feature selection was used to examine gyrification-sleep relationships. Results For most brain regions, greater lGI was associated with longer sleep duration, earlier sleep timing, lower variability in sleep regularity, and shorter time awake after sleep onset. lGI in frontoparietal network regions showed associations with sleep patterns that were stable across age. However, in default mode network regions, lGI was only associated with sleep patterns from late childhood through early-to-mid adolescence, a period of vulnerability for mental health disorders. Conclusions We detected both developmentally invariant and developmentally specific ties between local gyrification and naturalistic sleep patterns. Default mode network regions may be particularly susceptible to interventions promoting more optimal sleep during childhood and adolescence.

A parallel library of 108 4-aryl-1,4-dihydropyrimidine (DHPM) enantiomers, which are potential selectors for chiral HPLC separations, was synthesized using the single-step Biginelli multicomponent condensation. The individual compounds were screened by observing the enantioselectivity for resolution on a "brush-type" L-(3,5-dinitrobenzoyl)leucine-based chiral stationary phase, and separation factors alpha up to 12 were achieved. The best candidates from the library contained an ortho-substituted aromatic group at C4 carbon atom of the pyrimidine ring and an alkyl substituent at N1 nitrogen atom. Resolution of the enantiomers of the lead compound, 4-(9-phenanthryl)-DHPM 8, using semipreparative chiral HPLC followed by attachment to monodisperse macroporous aminomethacrylate beads, provided the novel polymer based chiral stationary phase with good enantioselectivities in the resolution of several pi-acidic aryl-dihydropyrimidines and derivatized profens. In addition, 3,5-dinitrobenzamido derivatives of alpha-amino acids could be resolved under normal phase HPLC conditions with separation factors up to 8.

When troubleshooting buggy executions of distributed systems, developers typically start by manually separating out events that are responsible for triggering the bug (signal) from those that are extraneous (noise). We present DEMi, a tool for automatically performing this minimization. We apply DEMi to buggy executions of two very different distributed systems, Raft and Spark, and find that it produces minimized executions that are between 1X and 4.6X the size of optimal executions.

Large-scale distributed systems, like MapReduce, are increasingly being used, but debugging such systems is still very difficult. In this paper, we propose D3, a new debugging system that answers diverse debugging queries by processing logs formally and efficiently. D3 specifies queries concisely in a declarative language and executes the queries in a distributed fashion, thereby lowering debugging overhead and bandwidth consumed. We demonstrate the effectiveness of our D3 design on a local cluster with Hadoop, an open-source MapReduce framework.

Network middleboxes must offer high availability, with automatic failover when a device fails. Achieving high availability is challenging because failover must correctly restore lost state (e.g., activity logs, port mappings) but must do so quickly (e.g., in less than typical transport timeout values to minimize disruption to applications) and with little overhead to failure-free operation (e.g., additional per-packet latencies of 10-100s of us). No existing middlebox design provides failover that is correct, fast to recover, and imposes little increased latency on failure-free operations. We present a new design for fault-tolerance in middleboxes that achieves these three goals. Our system, FTMB (for Fault-Tolerant MiddleBox), adopts the classical approach of "rollback recovery" in which a system uses information logged during normal operation to correctly reconstruct state after a failure. However, traditional rollback recovery cannot maintain high throughput given the frequent output rate of middleboxes. Hence, we design a novel solution to record middlebox state which relies on two mechanisms: (1) 'ordered logging', which provides lightweight logging of the information needed after recovery, and (2) a `parallel release' algorithm which, when coupled with ordered logging, ensures that recovery is always correct. We implement ordered logging and parallel release in Click and show that for our test applications our design adds only 30$\mu$s of latency to median per packet latencies. Our system introduces moderate throughput overheads (5-30%) and can reconstruct lost state in 40-275ms for practical systems.