Pd-Catalyzed Atroposelective C-H Olefination: Diverse Synthesis of Axially Chiral Biaryl-2-carboxylic Acids.

Axially chiral carboxylic acids are important motifs in chiral catalysts and ligands. We herein reported the synthesis of axially chiral carboxylic acids via Pd(II)-catalyzed atroposelective C-H olefination using carboxylic acid as the native directing group. A broad range of axial chiral biaryl-2-carboxylic acids were synthesized in good yields with high enantioselectivities (up to 84% yield with 99% ee). Gram-scale reaction and further transformation reactions also provide a platform for synthetic applications of this method.

Electrooxidative Rhodium(III)/Chiral Carboxylic Acid-Catalyzed Enantioselective C-H Annulation of Sulfoximines with Alkynes.

The combination of achiral Cp*Rh(III) with chiral carboxylic acids (CCAs) represents an efficient catalytic system in transition metal-catalyzed enantioselective C-H activation. However, this hybrid catalysis is limited to redox-neutral C-H activation reactions and the adopt to oxidative enantioselective C-H activation remains elusive and pose a significant challenge. Herein, we describe the development of an electrochemical Cp*Rh(III)-catalyzed enantioselective C-H annulation of sulfoximines with alkynes enabled by chiral carboxylic acid (CCA) in an operationally friendly undivided cell at room temperature. A broad range of enantioenriched 1,2-benzothiazines are obtained in high yields with excellent enantioselectivities (up to 99 % yield and 98 : 2 er). The practicality of this method is demonstrated by scale-up reaction in a batch reactor with external circulation. A crucial chiral Cp*Rh(III) intermediate is isolated, characterized, and transformed, providing rational support for a Rh(III)/Rh(I) electrocatalytic cycle.

Characterization of an ssDNA ligase and its application in aptamer circularization.

Aptamers are widely used in various biomedical areas as novel molecular recognition elements, however, short single-stranded DNA (ssDNA) or RNA oligonucleotides are easily degraded by nucleases in biological fluids. This problem can be solved by circularizing aptamers with circular ligases. Herein, a moderately thermostable ssDNA ligase was expressed and purified. The purified ligase showed good circularization activity for different length substrates and much higher circularization efficiency than T4 RNA ligase 1. Biochemical characterization revealed that the enzyme showed optimal circularization activity at pH 7.5 and 50 ᵒC. Mn2+ and Mg2+ increased enzyme circularization activity, with Mn2+ having higher activity than Mg2+. The optimal concentrations of Mn2+ and ligase were 1.25-2.5 mM and 0.02 nM, respectively. The kinetic parameters Km, Vmax and Kcat of ssDNA ligase were 1.16 µM, 10.71 µM/min, and 10.7 min-1, respectively. The ssDNA ligase efficiency was nucleotide-dependent, and 5'-G and 3'-T were the most ligase-favored terminal nucleotides. In addition, the affinity and stability of the circular aptamer were determined. The affinity constant (KD) was 4.9 µM, and the stability increased compared to its linear form. Molecular docking results showed that the circular aptamer bound to the target via two hydrogen bonds. This study provides a simple and efficient aptamer circularization modification method for improving aptamer stability and expanding its applications.

Nuclear spin polarization and control in hexagonal boron nitride.

Electron spins in van der Waals materials are playing a crucial role in recent advances in condensed-matter physics and spintronics. However, nuclear spins in van der Waals materials remain an unexplored quantum resource. Here we report optical polarization and coherent control of nuclear spins in a van der Waals material at room temperature. We use negatively charged boron vacancy ([Formula: see text]) spin defects in hexagonal boron nitride to polarize nearby nitrogen nuclear spins. We observe the Rabi frequency of nuclear spins at the excited-state level anti-crossing of [Formula: see text] defects to be 350 times larger than that of an isolated nucleus, and demonstrate fast coherent control of nuclear spins. Further, we detect strong electron-mediated nuclear-nuclear spin coupling that is five orders of magnitude larger than the direct nuclear-spin dipolar coupling, enabling multi-qubit operations. Our work opens new avenues for the manipulation of nuclear spins in van der Waals materials for quantum information science and technology.

High-Contrast Plasmonic-Enhanced Shallow Spin Defects in Hexagonal Boron Nitride for Quantum Sensing.

The recently discovered spin defects in hexagonal boron nitride (hBN), a layered van der Waals material, have great potential in quantum sensing. However, the photoluminescence and the contrast of the optically detected magnetic resonance (ODMR) of hBN spin defects are relatively low so far, which limits their sensitivity. Here we report a record-high ODMR contrast of 46% at room temperature and simultaneous enhancement of the photoluminescence of hBN spin defects by up to 17-fold by the surface plasmon of a gold film microwave waveguide. Our results are obtained with shallow boron vacancy spin defects in hBN nanosheets created by low-energy He+ ion implantation and a gold film microwave waveguide fabricated by photolithography. We also explore the effects of microwave and laser powers on the ODMR and improve the sensitivity of hBN spin defects for magnetic field detection. Our results support the promising potential of hBN spin defects for nanoscale quantum sensing.

Engineering Electron-Phonon Coupling of Quantum Defects to a Semiconfocal Acoustic Resonator.

Diamond-based microelectromechanical systems (MEMS) enable direct coupling between the quantum states of nitrogen-vacancy (NV) centers and the phonon modes of a mechanical resonator. One example, a diamond high-overtone bulk acoustic resonator (HBAR), features an integrated piezoelectric transducer and supports high-quality factor resonance modes into the gigahertz frequency range. The acoustic modes allow mechanical manipulation of deeply embedded NV centers with long spin and orbital coherence times. Unfortunately, the spin-phonon coupling rate is limited by the large resonator size, >100 µm, and thus strongly coupled NV electron-phonon interactions remain out of reach in current diamond BAR devices. Here, we report the design and fabrication of a semiconfocal HBAR (SCHBAR) device on diamond (silicon carbide) with f × Q > 1012 (>1013). The semiconfocal geometry confines the phonon mode laterally below 10 µm. This drastic reduction in modal volume enhances defect center coupling to a mechanical mode by 1000 times compared to prior HBAR devices. For the native NV centers inside the diamond device, we demonstrate mechanically driven spin transitions and show a high strain-driving efficiency with a Rabi frequency of (2π)2.19(14) MHz/Vp, which is comparable to a typical microwave antenna at the same microwave power, making SCHBAR a power-efficient device useful for fast spin control, dressed state coherence protection, and quantum circuit integration.

Ion Channels Involved in Substance P-Mediated Nociception and Antinociception.

Substance P (SP), an 11-amino-acid neuropeptide, has long been considered an effector of pain. However, accumulating studies have proposed a paradoxical role of SP in anti-nociception. Here, we review studies of SP-mediated nociception and anti-nociception in terms of peptide features, SP-modulated ion channels, and differential effector systems underlying neurokinin 1 receptors (NK1Rs) in differential cell types to elucidate the effect of SP and further our understanding of SP in anti-nociception. Most importantly, understanding the anti-nociceptive SP-NK1R pathway would provide new insights for analgesic drug development.

Evaluating the Potential of LJ1-01 Nighttime Light Data for Modeling Socio-Economic Parameters.

The LJ1-01 satellite is the first dedicated nighttime light remote sensing satellite in the world and offers a higher spatial resolution than the Defense Meteorological Satellite Program's Operational Linescan System (DMSP/OLS) and the Visible Infrared Imaging Radiometer Suite (VIIRS) sensor on the Suomi National Polar-orbiting Partnership (NPP) satellites of the United States. This study compared the LJ1-01 nighttime light data with NPP/VIIRS data in the context of modeling socio-economic parameters. In the eastern and central regions of China, 10 parameters from the four aspects of gross regional product (annual average population, electricity consumption, and area of land in use) were selected to build linear regression models. The results showed that the LJ1-01 nighttime light data offered better potential for modeling socio-economic parameters than the equivalent NPP/VIIRS data; the former can be an effective tool for establishing models for socio-economic parameters. There were significant positive correlations between the two types of nighttime light data and the 10 socio-economic parameters; that for the gross regional product was the highest.

Block Adjustment without GCPs for Chinese Spaceborne SAR GF-3 Imagery.

The Gaofen-3 (GF-3) satellite is the first C-band multi-polarization synthetic aperture radar (SAR) with the ability of high-accuracy mapping in China. However, the Ground Control Points (GCPs) are essential to ensure the accuracy of mapping for GF-3 SAR imagery at present. In this paper, we analyze the error sources that affect the geometric processing and propose a new block adjustment method without GCPs for GF-3 SAR imagery. Firstly, the geometric calibration of GF-3 image is carried out. Secondly, the rational polynomial coefficient (RPC) model is directly generated after the geometric calibration parameters compensation of each image. Finally, we solve the orientation parameters of the GF-3 images through DEM assisted planar block adjustment and conduct ortho-rectification. With two different imaging modes of GF-3 satellite, which include the QPSI and FS2, we carry out the block adjustment without GCPs. Experimental results of testing areas including Wuhan city and Hubei province in China show that the geometric mosaic accuracy and the absolute positioning accuracy of the orthophoto are better than one pixel, which has laid a good foundation for the application of GF-3 image in global high-accuracy mapping.

Acid-sensing ion channels: dual function proteins for chemo-sensing and mechano-sensing.

BACKGROUND: Acid-sensing ion channels (ASICs) are a group of amiloride-sensitive ligand-gated ion channels belonging to the family of degenerin/epithelial sodium channels. ASICs are predominantly expressed in both the peripheral and central nervous system and have been characterized as potent proton sensors to detect extracellular acidification in the periphery and brain. MAIN BODY: Here we review the recent studies focusing on the physiological roles of ASICs in the nervous system. As the major acid-sensing membrane proteins in the nervous system, ASICs detect tissue acidosis occurring at tissue injury, inflammation, ischemia, stroke, and tumors as well as fatiguing muscle to activate pain-sensing nerves in the periphery and transmit pain signals to the brain. Arachidonic acid and lysophosphocholine have been identified as endogenous non-proton ligands activating ASICs in a neutral pH environment. On the other hand, ASICs are found involved in the tether model mechanotransduction, in which the extracellular matrix and cytoplasmic cytoskeletons act like a gating-spring to tether the mechanically activated ion channels and thus transmit the stimulus force to the channels. Accordingly, accumulating evidence has shown ASICs play important roles in mechanotransduction of proprioceptors, mechanoreceptors and nociceptors to monitor the homoeostatic status of muscle contraction, blood volume, and blood pressure as well as pain stimuli. CONCLUSION: Together, ASICs are dual-function proteins for both chemosensation and mechanosensation involved in monitoring physiological homoeostasis and pathological signals.