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51.
Zhen Zhang Sneha Ray Leah Imlay Lauren T. Callaghan Hanspeter Niederstrasser Prema Latha Mallipeddi Bruce A. Posner Dawn M. Wetzel Margaret A. Phillips Myles W. Smith 《Chemical science》2021,12(30):10388
The spiroindimicins are a unique class of chlorinated indole alkaloids characterized by three heteroaromatic rings structured around a congested spirocyclic stereocenter. Here, we report the first total synthesis of (+)-spiroindimicin A, which bears a challenging C-3′/C-5′′-linked spiroindolenine. We detail our initial efforts to effect a biomimetic oxidative spirocyclization from its proposed natural precursor, lynamicin D, and describe how these studies shaped our final abiotic 9-step solution to this complex alkaloid built around a key Pd-catalyzed asymmetric spirocyclization. Scalable access to spiroindimicins A, H, and their congeners has enabled discovery of their activity against several parasites relevant to human health, providing potential starting points for new therapeutics for the neglected tropical diseases leishmaniasis and African sleeping sickness.Spiroindimicins A and H have been synthesized for the first time via a key palladium-catalyzed spirocyclization. Access to these alkaloids and several congeners has allowed the discovery of their antiparasitic properties. 相似文献
52.
C Wright R Leyden PV Murphy M Callaghan T Velasco-Torrijos S McClean 《Molecules (Basel, Switzerland)》2012,17(9):10065-10071
Burkholderia cepacia complex (Bcc) is an opportunistic pathogen in cystic fibrosis patients which is inherently resistant to antimicrobial agents. The mechanisms of attachment and pathogenesis of Bcc, a group of 17 species, are poorly understood. The most commonly identified Bcc species in newly colonised patients, Burkholderia multivorans, continues to be acquired from the environment. Development of therapies which can prevent or reduce the risk of colonization on exposure to Bcc in the environment would be a better alternative to antimicrobial agents. Previously, it has been shown that Bcc strains bound to many glycolipid receptors on lung epithelia. Using a real-time PCR method to quantify the levels of binding of B. multivorans to the lung epithelial cells, we have examined glycoconjugate derivatives for their potential to inhibit host cell attachment. Bivalent lactosides previously shown to inhibit galectin binding significantly reduced the attachment of B. multivorans to CF lung epithelial cells at micromolar concentrations. This was in contrast to monosaccharides and lactose, which were only effective in the millimolar range. Development of glycoconjugate therapies such as these, which inhibit attachment to lung epithelial cells, represent an alternative means of preventing infection with inherently antimicrobially resistant pathogens such as B. multivorans. 相似文献
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The electromagnet provides a favorable environment for certain applications of NMR microscopy. These include plant imaging experiments and measurements of slow molecular diffusion, where high magnetic field gradients for the pulsed gradient spin echo (PGSE) technique are required. In this paper, two probes designed specifically for these two applications are described. In the first case, the open space within the probe has been maximized in order to incorporate environmental support systems for the plant, while in the second the smallest possible PGSE gradient coil former has been used to maximize the gradient strength. Examples are given of Dynamic NMR Microscopy experiments on a castor bean stem and on poly(ethylene oxide)/water solutions under shear thinning conditions. 相似文献
56.
Hubbard PL McGrath KM Callaghan PT 《Langmuir : the ACS journal of surfaces and colloids》2006,22(9):3999-4003
Diffusion-diffusion correlation measurements by NMR are used to investigate the degree of orientational order in the lamellar phase of Aerosol OT (bis(2-ethylhexyl) sodium sulfosuccinate) and water at a range of surfactant concentrations (25, 33, and 50 wt %). We show that true isotropy of the domains is found at the lowest concentration but that at higher concentrations deviations from isotropy can be found, as evidenced by asymmetry on the 2D correlation distributions. We further discuss the significance of asymmetry in diffusion-diffusion exchange experiments, 2D distributions that should always be symmetric in steady state. 相似文献
57.
Lefebvre J Callaghan F Katz MJ Sonier JE Leznoff DB 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(26):6748-6761
The structures of two cyanoaurate-based coordination polymers, M(mu-OH(2))(2)[Au(CN)(2)](2) (M=Cu, Ni), were determined by using a combination of powder and single-crystal X-ray diffraction techniques. The basic structural motif for both polymers contains rarely observed M(mu-OH(2))(2)M double aqua-bridges, which generate an infinite chain; two trans [Au(CN)(2)](-) units also dangle from each metal center. The chains form ribbons that interact three dimensionally through CNH hydrogen bonding. The magnetic properties of both compounds and of the dehydrated analogue Cu[Au(CN)(2)](2) were investigated by direct current (dc) and alternating current (ac) magnetometry; muon spin-relaxation data was also obtained to probe their magnetic properties in zero-field. In M(mu-OH(2))(2)[Au(CN)(2)](2), ferromagnetic chains of M(mu-OH(2))(2)M are present below 20 K. Interchain magnetic interactions mediated through hydrogen bonding, involving water and cyanoaurate units, yield a long-range magnetically ordered system in Cu(mu-OH(2))(2)[Au(CN)(2)](2) below 0.20 K, as indicated by precession in the muon spin polarization decay. Ni(mu-OH(2))(2)[Au(CN)(2)](2) undergoes a transition to a spin-glass state in zero-field at 3.6 K, as indicated by a combination of muon spin-relaxation and ac-susceptibility data. This transition is probably due to competing interactions that lead to spin frustration. A phase transition to a paramagnetic state is possible for Ni(mu-OH(2))(2)[Au(CN)(2)](2) upon application of an external field; the critical field was determined to be 700 Oe at 1.8 K. The dehydrated compound Cu[Au(CN)(2)](2) shows weak antiferromagnetic interactions at low temperatures. 相似文献
58.
Manz B Coy A Dykstra R Eccles CD Hunter MW Parkinson BJ Callaghan PT 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2006,183(1):25-31
A new portable NMR sensor with a novel one-sided access magnet design, termed NMR-MOLE (MObile Lateral Explorer), has been characterised in terms of sensitivity and depth penetration. The magnet has been designed to be portable and create a volume with a relatively homogeneous magnetic field, 15,000 ppm over a region from 4 to 16 mm away from the probe, with maximum sensitivity at a depth of 10 mm. The proton NMR frequency is 3.3 MHz. We have demonstrated that with this approach a highly sensitive, portable, unilateral NMR sensor can be built. Such a design is especially suited for the characterisation of liquids in situations where unilateral or portable access is required. 相似文献
59.
Dynamic nuclear polarization (DNP) is introduced as a powerful tool for polarization enhancement in multi-dimensional Earth’s field NMR spectroscopy. Maximum polarization enhancements, relative to thermal equilibrium in the Earth’s magnetic field, are calculated theoretically and compared to the more traditional prepolarization approach for NMR sensitivity enhancement at ultra-low fields. Signal enhancement factors on the order of 3000 are demonstrated experimentally using DNP with a nitroxide free radical, TEMPO, which contains an unpaired electron which is strongly coupled to a neighboring 14N nucleus via the hyperfine interaction. A high-quality 2D 19F–1H COSY spectrum acquired in the Earth’s magnetic field with DNP enhancement is presented and compared to simulation. 相似文献
60.
The interaction energies between PS, Pα-MS, and PMMA, as well as acrylonitrile and maleic anhydride units, with a series of polysulfones were quantitatively determined from oligomer/oligomer, oligomer/homopolymer, and homopolymer/copolymer blends. Interaction energies were calculated from the Flory-Huggins theory and the Sanchez-Lacombe equation of state theory using experimental cloud points or miscibility boundaries. Alkyl addition to the phenyl rings of polysulfone is favorable for miscibility with polystyrene whereas halogenation of the bisphenol connector unit favors miscibility with poly(methyl methacrylate). Interaction energies are quantitatively ranked and described qualitatively in terms of changes in the electronic charge distribution of the polymer repeat units as calculated by SYBYL software. © 1994 John Wiley & Sons, Inc. 相似文献