We experimentally demonstrate the use of a single electronic spin to measure the quantum dynamics of distant individual nuclear spins from within a surrounding spin bath. Our technique exploits ...coherent control of the electron spin, allowing us to isolate and monitor nuclear spins weakly coupled to the electron spin. Specifically, we detect the evolution of distant individual 13C nuclear spins coupled to single nitrogen vacancy centers in a diamond lattice with hyperfine couplings down to a factor of 8 below the electronic spin bare dephasing rate. Potential applications to nanoscale magnetic resonance imaging and quantum information processing are discussed.
Difunctionalization reactions of C-C σ-bonds have the potential to streamline access to molecules that would otherwise be difficult to prepare. However, the development of such reactions is ...challenging because C-C σ-bonds are typically unreactive. Exploiting the high ring-strain energy of polycyclic carbocycles is a common strategy to weaken and facilitate the reaction of C-C σ-bonds, but there are limited examples of highly strained C-C σ-bonds being used in difunctionalization reactions. We demonstrate that highly strained bicyclo1.1.0butyl boronate complexes (strain energy ca. 65 kcal/mol), which were prepared by reacting boronic esters with bicyclo1.1.0butyl lithium, react with electrophiles to achieve the diastereoselective difunctionalization of the strained central C-C σ-bond of the bicyclo1.1.0butyl unit. The reaction shows broad substrate scope, with a range of different electrophiles and boronic esters being successfully employed to form a diverse set of 1,1,3-trisubstituted cyclobutanes (>50 examples) with high diastereoselectivity. The high diastereoselectivity observed has been rationalized based on a combination of experimental data and DFT calculations, which suggests that separate concerted and stepwise reaction mechanisms are operating, depending upon the migrating substituent and electrophile used.
The blood-brain barrier (BBB), blood-spinal cord barrier (BSCB), and blood-cerebrospinal fluid barrier (BCSFB) control cerebral/spinal cord homeostasis by selective transport of molecules and cells ...from the systemic compartment. In the spinal cord and brain of both ALS patients and animal models, infiltration of T-cell lymphocytes, monocyte-derived macrophages and dendritic cells, and IgG deposits have been observed that may have a critical role in motor neuron damage. Additionally, increased levels of albumin and IgG have been found in the cerebrospinal fluid in ALS patients. These findings suggest altered barrier permeability in ALS. Recently, we showed disruption of the BBB and BSCB in areas of motor neuron degeneration in the brain and spinal cord in G93A SOD1 mice modeling ALS at both early and late stages of disease using electron microscopy. Examination of capillary ultrastructure revealed endothelial cell degeneration, which, along with astrocyte alteration, compromised the BBB and BSCB. However, the effect of these alterations upon barrier function in ALS is still unclear. The aim of this study was to determine the functional competence of the BSCB in G93A mice at different stages of disease.
Evans Blue (EB) dye was intravenously injected into ALS mice at early or late stage disease. Vascular leakage and the condition of basement membranes, endothelial cells, and astrocytes were investigated in cervical and lumbar spinal cords using immunohistochemistry. Results showed EB leakage in spinal cord microvessels from all G93A mice, indicating dysfunction in endothelia and basement membranes and confirming our previous ultrastructural findings on BSCB disruption. Additionally, downregulation of Glut-1 and CD146 expressions in the endothelial cells of the BSCB were found which may relate to vascular leakage.
Results suggest that the BSCB is compromised in areas of motor neuron degeneration in ALS mice at both early and late stages of the disease.
Mechanical systems can be influenced by a wide variety of small forces, ranging from gravitational to optical, electrical, and magnetic. When mechanical resonators are scaled down to nanometer-scale ...dimensions, these forces can be harnessed to enable coupling to individual quantum systems. We demonstrate that the coherent evolution of a single electronic spin associated with a nitrogen vacancy center in diamond can be coupled to the motion of a magnetized mechanical resonator. Coherent manipulation of the spin is used to sense driven and Brownian motion of the resonator under ambient conditions with a precision below 6 picometers. With future improvements, this technique could be used to detect mechanical zero-point fluctuations, realize strong spin-phonon coupling at a single quantum level, and implement quantum spin transducers.
Dihydrobenzofurans and indolines are important constituents of pharmaceuticals. Herein, we describe a novel strategy for their construction in which the aromatic ring is created de novo through an ...inverse-electron demand Diels–Alder reaction and cheletropic extrusion sequence of a 2-halothiophene-1,1-dioxide with an enol ether/enamide, followed by aromatization. Unusually, the aromatization process proved to be highly challenging, but it was discovered that treatment of the halocyclohexadienes with a base effected an α-elimination–aromatization reaction. Mechanistic investigation of this step using deuterium-labeling studies indicated the intermediacy of a carbene which undergoes a 1,2-hydrogen shift and subsequent aromatization. The methodology was applied to a modular and stereoselective total synthesis of the antiplatelet drug beraprost in only 8 steps from a key enal-lactone. This lactone provided the core of beraprost to which both its sidechains could be appended through a 1,4-conjugate addition process (lower ω-sidechain), followed by de novo construction of beraprost’s dihydrobenzofuran (upper α-sidechain) using our newly developed methodology. Additionally, we have demonstrated the breadth of our newly established protocol in the synthesis of functionalized indolines, which occurred with high levels of regiocontrol. According to density-functional theory (DFT) calculations, the high selectivity originates from attractive London dispersion interactions in the TS of the Diels–Alder reaction.
Prostaglandins have been attractive targets in total synthesis for over 50 years, resulting in the development of new synthetic strategies and methodologies that have served the broader chemical ...community. However, these molecules are not just of academic interest, a number of prostaglandin analogues are used in the clinic, and some are even on the WHO list of essential medicines. In this personal account, we describe our own approach to the family of prostaglandins, which centers around the synthesis of a key enal intermediate, formed from the l‐proline catalysed dimerization of succinaldehyde. We highlight the discovery and further optimization of this key reaction, its scale up, and subsequent application to a range of prostaglandins.
This review describes the discovery and optimization of the l‐proline catalysed aldol dimerization of succinaldehyde to give a key enal intermediate, and its subsequent application to a range of prostaglandins.
We report a pressure study of the metamagnetic/ferroelectric hybrid heterostructure of a quenched FeRh thin film (25 nm) grown on single crystal barium titanate (BTO). It has been previously reported ...that when the BTO undergoes a crystal transition a massive magnetization and coercivity change is triggered in the highly strain sensitive quenched FeRh thin film. Therefore quenched FeRh makes for an ideal probe for mapping a materials structural phase transitions. In this work we demonstrate this effect as a function of both temperature and hydrostatic pressure. As a result, we present the pressure dependence of the hybrid material which aligns identically with the BTO substrates pressure dependence reported in literature. The concept of combining a structural phase transitional (SPT) material with a magnetostrictive magnetic metal has been shown with vanadium oxides and our findings here prove that this methodology can be extended to strain sensitive metamagnetic materials systems in thin film, and possibly in bulk, heterostructures.
Point defects, such as oxygen vacancies, control the physical properties of complex oxides, relevant in active areas of research from superconductivity to resistive memory to catalysis. In most oxide ...semiconductors, electrons that are associated with oxygen vacancies occupy the conduction band, leading to an increase in the electrical conductivity. Here we demonstrate, in contrast, that in the correlatedelectron perovskite rare-earth nickelates, RNiO₃ (R is a rare-earth element such as Sm or Nd), electrons associated with oxygen vacancies strongly localize, leading to a dramatic decrease in the electrical conductivity by several orders of magnitude. This unusual behavior is found to stem from the combination of crystal field splitting and filling-controlled Mott–Hubbard electron–electron correlations in the Ni 3d orbitals. Furthermore, we show the distribution of oxygen vacancies in NdNiO₃ can be controlled via an electric field, leading to analog resistance switching behavior. This study demonstrates the potential of nickelates as testbeds to better understand emergent physics in oxide heterostructures as well as candidate systems in the emerging fields of artificial intelligence.
Due to its proximity to room temperature and demonstrated high degree of temperature tunability, FeRh's metamagnetic ordering transition is attractive for novel high-performance computing devices ...seeking to use magnetism as the state variable. We demonstrate electrical control of the antiferromagnetic-to-ferromagnetic transition via Joule heating in FeRh wires. The magnetic transition of FeRh is accompanied by a change in resistivity, which can be probed electrically and allows for integration into switching devices. Finite element simulations based on abrupt state transition within each domain result in a globally smooth transition that agrees with the experimental findings and provides insight into the thermodynamics involved. We measure a 150 K decrease in transition temperature with currents up to 60 mA, limited only by the dimensions of the device. The sizeable shift in transition temperature scales with current density and wire length, suggesting the absolute resistance and heat dissipation of the substrate are also important. The FeRh phase change is evaluated by pulsed I-V using a variety of bias conditions. We demonstrate high speed (~ ns) memristor-like behavior and report device performance parameters such as switching speed and power consumption that compare favorably with state-of-the-art phase change memristive technologies.
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