Access to Nitrogen Heterocycles via Borrowing Hydrogen Catalysis

Nitrogen heterocycles are ubiquitous motifs which occur as the core structure of several alkaloid natural products exhibiting inherent biological activity against an array of bacteria, fungi, viruses, and cancer cell lines. These azacycles serve as key synthetic building blocks for medicinal chemists to access more structurally complex and diverse compounds with tunable biological properties. A synthetic approach to these valuable motifs employing intramolecular borrowing hydrogen catalysis has been developed. The utility of the developed chemistry will be applied to synthetic efforts towards the recently isolated Cylicomorphins A-E

Learning When to Speak: Latency and Quality Trade-offs for Simultaneous Speech-to-Speech Translation with Offline Models

Recent work in speech-to-speech translation (S2ST) has focused primarily on offline settings, where the full input utterance is available before any output is given. This, however, is not reasonable in many real-world scenarios. In latency-sensitive applications, rather than waiting for the full utterance, translations should be spoken as soon as the information in the input is present. In this work, we introduce a system for simultaneous S2ST targeting real-world use cases. Our system supports translation from 57 languages to English with tunable parameters for dynamically adjusting the latency of the output -- including four policies for determining when to speak an output sequence. We show that these policies achieve offline-level accuracy with minimal increases in latency over a Greedy (wait-$k$) baseline. We open-source our evaluation code and interactive test script to aid future SimulS2ST research and application development.Comment: To appear at INTERSPEECH 202

Van der Waals Engineering of Ferromagnetic Semiconductor Heterostructures for Spin and Valleytronics

The integration of magnetic material with semiconductors has been fertile ground for fundamental science as well as of great practical interest toward the seamless integration of information processing and storage. Here we create van der Waals heterostructures formed by an ultrathin ferromagnetic semiconductor CrI3 and a monolayer of WSe2. We observe unprecedented control of the spin and valley pseudospin in WSe2, where we detect a large magnetic exchange field of nearly 13 T and rapid switching of the WSe2 valley splitting and polarization via flipping of the CrI3 magnetization. The WSe2 photoluminescence intensity strongly depends on the relative alignment between photo-excited spins in WSe2 and the CrI3 magnetization, due to ultrafast spin-dependent charge hopping across the heterostructure interface. The photoluminescence detection of valley pseudospin provides a simple and sensitive method to probe the intriguing domain dynamics in the ultrathin magnet, as well as the rich spin interactions within the heterostructure.Comment: Supplementary Materials included. To appear in Science Advance

Electrical Control of 2D Magnetism in Bilayer CrI3

The challenge of controlling magnetism using electric fields raises fundamental questions and addresses technological needs such as low-dissipation magnetic memory. The recently reported two-dimensional (2D) magnets provide a new system for studying this problem owing to their unique magnetic properties. For instance, bilayer chromium triiodide (CrI3) behaves as a layered antiferromagnet with a magnetic field-driven metamagnetic transition. Here, we demonstrate electrostatic gate control of magnetism in CrI3 bilayers, probed by magneto-optical Kerr effect (MOKE) microscopy. At fixed magnetic fields near the metamagnetic transition, we realize voltage-controlled switching between antiferromagnetic and ferromagnetic states. At zero magnetic field, we demonstrate a time-reversal pair of layered antiferromagnetic states which exhibit spin-layer locking, leading to a remarkable linear dependence of their MOKE signals on gate voltage with opposite slopes. Our results pave the way for exploring new magnetoelectric phenomena and van der Waals spintronics based on 2D materials.Comment: To appear in Nature Nanotechnolog

A Laboratory Study of C_3H^+ and the C_3H Radical in Three New Vibrationally Excited ^2Σ States Using a Pin-Hole Nozzle Discharge Source

Rotational lines of the positive molecular ion C_3H^+ and of the neutral C_3H radical in three new vibrationally excited states with ^2Σ symmetry have been detected in a supersonic molecular beam in the centimeter-wave band. The fundamental rotational line of the ion is quite weak, but is observed with similar intensity in a dc discharge through several different hydrocarbon gases when helium is the buffer gas. Under these conditions, the fractional abundance of C_3H^+ relative to C_3H is estimated to be of order 10^(−4), i.e., toward the lower end of the ratio (10^(−3)–10^(−4)) found for protonated ions using the same discharge nozzle. For each new ^2Σ state of the C_3H radical, spectroscopic constants, including those describing hydrogen hyperfine structure, have been determined to high precision. Lines of one ^2Σ state (B = 11271 MHz) are particularly intense in our molecular beam; for this state and a second one (B = 11306 MHz), millimeter-wave transitions have also been observed between 180 and 340 GHz using a long path dc glow absorption spectrometer. On the basis of intensity measurements with this spectrometer, the inferred rotation–vibration constant α, and theoretical calculations, the state with B = 11271 MHz is tentatively assigned to the ν_5 bending mode, predicted to lie ~300 cm^(−1) above ground

Expectations of Success as a Predictor of Negative Symptom Reduction over 18 months in Individuals with Schizophrenia

Negative symptoms are often enduring and lead to poor functional outcomes in individuals with schizophrenia. The cognitive model of negative symptoms proposes that low expectancies of success contribute to the development and maintenance of negative symptoms; however, longitudinal investigations assessing these beliefs and negative symptoms are needed. The current study examined whether an individual’s baseline expectancies of success – one’s beliefs about future success and goal attainment – predicted negative symptoms reduction over 18 months in individuals with schizophrenia-spectrum disorders (n=118). Data were collected at baseline, 9 months, and 18 months as part of a randomized controlled trial of Illness Management and Recovery. A mixed effects regression analysis revealed a significant reduction in negative symptoms over time, with a significant interaction effect between time and baseline expectancies of success. After controlling for baseline negative symptoms, demographic variables, and treatment conditions, those with high and moderate baseline expectancies of success evidenced a significant reduction in negative symptoms at 18 months, while those with low baseline expectancies of success did not evidence reduced negative symptoms. Findings support the cognitive model of negative symptoms and suggest that expectancies of success may be a useful treatment target for interventions aimed at reducing negative symptoms

Flexible Supervised Autonomy for Exploration in Subterranean Environments

While the capabilities of autonomous systems have been steadily improving in recent years, these systems still struggle to rapidly explore previously unknown environments without the aid of GPS-assisted navigation. The DARPA Subterranean (SubT) Challenge aimed to fast track the development of autonomous exploration systems by evaluating their performance in real-world underground search-and-rescue scenarios. Subterranean environments present a plethora of challenges for robotic systems, such as limited communications, complex topology, visually-degraded sensing, and harsh terrain. The presented solution enables long-term autonomy with minimal human supervision by combining a powerful and independent single-agent autonomy stack, with higher level mission management operating over a flexible mesh network. The autonomy suite deployed on quadruped and wheeled robots was fully independent, freeing the human supervision to loosely supervise the mission and make high-impact strategic decisions. We also discuss lessons learned from fielding our system at the SubT Final Event, relating to vehicle versatility, system adaptability, and re-configurable communications.Comment: Field Robotics special issue: DARPA Subterranean Challenge, Advancement and Lessons Learned from the Final