Oxidant-controlled regioselectivity in the oxidative arylation of N-acetylindoles

N-Acetylindoles can be oxidatively coupled with arenes such as benzene or pentafluorobenzene in dioxane. The use of Cu(OAc)2 as the stoichiometric oxidant produces selective arylation at the 3-position of indole while AgOAc produces selective arylation at indole’s 2-position. [Refer to PDF for graphical abstract

Cyclodextrin-Based Contrast Agents for Medical Imaging

Cyclodextrins (CDs) are naturally occurring cyclic oligosaccharides consisting of multiple glucose subunits. CDs are widely used in host–guest chemistry and biochemistry due to their structural advantages, biocompatibility, and ability to form inclusion complexes. Recently, CDs have become of high interest in the field of medical imaging as a potential scaffold for the development of a large variety of the contrast agents suitable for magnetic resonance imaging, ultrasound imaging, photoacoustic imaging, positron emission tomography, single photon emission computed tomography, and computed tomography. The aim of this review is to summarize and highlight the achievements in the field of cyclodextrin-based contrast agents for medical imaging

In Vivo Detection of Cucurbit[6]uril, a Hyperpolarized Xenon Contrast Agent for a Xenon Magnetic Resonance Imaging Biosensor

The Hyperpolarized gas Chemical Exchange Saturation Transfer (HyperCEST) Magnetic Resonance (MR) technique has the potential to increase the sensitivity of a hyperpolarized xenon-129 MRI contrast agent. Signal enhancement is accomplished by selectively depolarizing the xenon within a cage molecule which, upon exchange, reduces the signal in the dissolved phase pool. Herein we demonstrate the in vivodetection of the cucurbit[6]uril (CB6) contrast agent within the vasculature of a living rat. Our work may be used as a stepping stone towards using the HyperCEST technique as a molecular imaging modality

Seasonal changes in eastern hemlock (\u3cem\u3eTsuga canadensis\u3c/em\u3e) foliar chemistry

Eastern hemlock (Tsuga canadensis (L.) Carriére; hemlock) is an eastern North American conifer threatened by the invasive hemlock woolly adelgid (Adelges tsugae Annand). Changes in foliar terpenes and phenolics were evaluated in new (current year growth) and mature (1-year old growth) hemlock needles during the growing season and into plant dormancy. From April through September, foliar concentrations of non-volatile soluble phenolics, condensed tannins, lignin, mono- and sesquiterpenes α-pinene, camphene, isobornyl acetate, and diterpene resin were quantified. After September, additional analyses of metabolites that continued to differ significantly in new versus mature foliage were carried out. Total soluble phenolic concentration and condensed tannin concentration in new foliage remained low relative to mature foliage throughout the growing season and converged in December. Lignin concentration in new foliage converged with that of mature foliage by July. Concentrations of α-pinene, camphene, isobornyl acetate, and diterpene resin in new foliage converged with mature foliage within one month of budbreak. The convergence of terpene concentrations in new and mature foliage suggests that these metabolites may play a role in herbivore defense during the peak growing season. Conversely, soluble phenolics, including condensed tannins, may defend foliage from herbivory outside of the spring growth period

Decacationic Pillar[5]arene: A New Scaffold for the Development of 129Xe MRI Imaging Agents

A decacationic water-soluble pillar[5]arene possessing a nonsolvated hydrophobic core has been designed and synthesized. This supramolecular host is capable of binding xenon, as evidenced by hyperCEST depletion experiments. Fluorescence-based studies also demonstrate that xenon binds into the cavity of the pillararene with an association constant of 4.6 × 103 M−1. These data indicate that the water-soluble pillararene is a potential scaffold for building contrast agents that can be detected by xenon-129 magnetic resonance imaging

HyperCEST detection of cucurbit[6]uril in whole blood using an ultrashort saturation Pre-pulse train

Xenon based biosensors have the potential to detect and localize biomarkers associated with a wide variety of diseases. The development and nuclear magnetic resonance (NMR) characterization of cage molecules which encapsulate hyperpolarized xenon is imperative for the development of these xenon biosensors. We acquired 129Xe NMR spectra, and magnetic resonance images and a HyperCEST saturation map of cucurbit[6]uril (CB6) in whole bovine blood. We observed a mean HyperCEST depletion of 84% (n = 5) at a concentration of 5 mM and 74% at 2.5 mM. Additionally, we collected these data using a pulsed HyperCEST saturation pre-pulse train with a SAR of 0.025 W/kg which will minimize any potential RF heating in animal or human tissue. Copyright © 2016 John Wiley & Sons, Ltd

Cyclodextrin-Based Pseudorotaxanes: Easily Conjugatable Scaffolds for Synthesizing Hyperpolarized Xenon-129 Magnetic Resonance Imaging Agents

Hyperpolarized (HP) xenon-129 (Xe) magnetic resonance (MR) imaging has the potential to detect biological analytes with high sensitivity and high resolution when coupled with xenon-encapsulating molecular probes. Despite the development of numerous HP Xe probes, one of the challenges that has hampered the translation of these agents from in vitro demonstration to in vivo testing is the difficulty in synthesizing the Xe-encapsulating cage molecule. In this study, we demonstrate that a pseudorotaxane, based on a γ-cyclodextrin macrocycle, is easily synthesized in one step and is detectable using HyperCEST-enhanced ¹²⁹Xe MR spectroscopy