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91.
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Site‐Selective,Late‐Stage C−H 18F‐Fluorination on Unprotected Peptides for Positron Emission Tomography Imaging
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Dr. Zheliang Yuan Dr. Matthew B. Nodwell Dr. Hua Yang Dr. Noeen Malik Helen Merkens Dr. François Bénard Dr. Rainer E. Martin Dr. Paul Schaffer Prof. Robert Britton 《Angewandte Chemie (International ed. in English)》2018,57(39):12733-12736
Peptides are often ideal ligands for diagnostic molecular imaging due to their ease of synthesis and tuneable targeting properties. However, labelling unmodified peptides with 18F for positron emission tomography (PET) imaging presents a number of challenges. Here we show the combination of photoactivated sodium decatungstate and [18F]‐N‐fluorobenzenesulfonimide effects site‐selective 18F‐fluorination at the branched position in leucine residues in unprotected and unaltered peptides. This streamlined process provides a means to directly convert native peptides into PET imaging agents under mild aqueous conditions, enabling rapid discovery and development of peptide‐based molecular imaging tools. 相似文献
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John F Valliant Paul Schaffer Karin A Stephenson James F Britten 《The Journal of organic chemistry》2002,67(2):383-387
A nido-carborane analogue of tamoxifen, the widely employed breast cancer therapy agent, was prepared as an archetype of a potential new class of antiestrogen and boron neutron capture therapy agent in which the carborane is incorporated within the framework of the parent compound. The carborane was introduced through the reaction of 6,9-bis(acetonitrile)decaborane with a unique and highly conjugated ene-yne, which was prepared stereoselectively. NMR spectroscopy and a crystal structure of a key intermediate, the carborane analogue of chloro-tamoxifen, demonstrated the structural similarities between the tamoxifen carboranes and their corresponding phenyl analogues. 相似文献
96.
Valliant JF Sogbein OO Morel P Schaffer P Guenther KJ Bain AD 《Inorganic chemistry》2002,41(10):2731-2737
Protected hydrazine derivatives of ortho-, meta-, and para-carboranes were synthesized in good to excellent yields by reacting the mono-lithio salts of the respective carboranes with di-tert-butyl azodicarboxylate (DBAD). Subsequent deprotonation of the remaining carborane CH group, followed by the addition of CO(2)(g), resulted in the formation of bifunctional C-hydrazino-C-carboxycarboranes in good to excellent overall yields. Crystal structures of the monosubstituted ortho-carborane, 1-[(N,N'((tert-butyloxy)carbonyl)hydrazino)]-1,2-dicarba-closo-dodecaborane (8) [a = 21.213(6) A, b = 10.498(3) A, c = 9.866(2) A, alpha = gamma = 90 degrees, beta = 90.529(4) degrees ] and the bifunctional para-carborane 1-[(N,N'((tert-butyloxy)carbonyl)hydrazino)]-1,12-dicarba-closo-dodecaborane-12-carboxylic acid (3) [a = 12.744(10) A, b = 12.875(9) A, c = 14.767(9) A, alpha = beta = gamma = 90 degrees ] were obtained. Intermolecular hydrogen bonding was a dominant packing feature in both structures. The reported compounds represent a unique class of bifunctional carboranes that can be used in peptidomimetic research and as synthons to prepare novel radiopharmaceuticals and boron neutron capture therapy/boron neutron capture synovectomy (BNCT/BNCS) agents. 相似文献
97.
J. W. Kooi M. Chan B. Bumble H. G. LeDuc P. L. Schaffer T. G. Phillips 《International Journal of Infrared and Millimeter Waves》1994,15(5):783-805
We report recent results on a 20% reduced height 270–425 GHz SIS waveguide receiver employing a 0.49 µm2 Nb/AlO
x
/Nb tunnel junction. A 50% operating bandwidth is achieved by using a RF compensated junction mounted in a two-tuner reduced height waveguide mixer block. The junction uses an end-loaded tuning stub with two quarter-wave transformer sections. We demonstrate that the receiver can be tuned to give 0–2 dB of conversion gain and 50–80% quantum efficiency over parts of it's operating range. The measured instantaneous bandwidth of the receiver is 25 GHz which ensures virtually perfect double sideband mixer response. Best noise temperatures are typically obtained with a mixer conversion loss of 0.5 to 1.5 dB giving uncorrected receiver and mixer noise temperatures of 50K and 42K respectively at 300 and 400 GHz. The measured double sideband receiver noise temperature is less than 100K from 270 GHz to 425 GHz with a best value of 48K at 376 GHz, within a factor of five of the quantum limit. The 270–425 GHz receiver has a full 1 GHz IF passband and has been successfully installed at the Caltech Submillimeter Observatory in Hawaii. Preliminary tests of a similar junction design in a full height 230 GHz mixer block indicate large conversion gain and receiver noise temperatures below 50K DSB from 200–300 GHz. Best operation is again achieved with the mixer tuned for 0.5–1.5 dB conversion loss which at 258 GHz resulted in receiver and mixer noise temperature of 34K and 27K respectively. 相似文献
98.
Retroviral and lentiviral based gene delivery vectors have been used in numerous pre-clinical studies and clinical trials due to their advantages, including stable and prolonged expression of therapeutic transgenes and minimal immune responses against the vector. Despite such advantages, however, retroviral vectors also have several limitations for gene therapy applications. For example, they can suffer from a lack of efficient or targeted gene delivery to key cell types. In addition, retroviral vector stability can be compromised by their envelope proteins. This review briefly describes how such limitations have been overcome by recently developed library selection approaches that borrow a lesson from nature: the ability of evolution to generate biomolecules with novel function. These library selection approaches are based on the construction of retroviral libraries where the sequences encoding natural viral components are partially randomized using a variety of methods in order to generate diverse libraries that can be selected to create improved or novel functions. These high throughput, library-based approaches provide a strong complement to rational engineering of viral components for the rapid development of efficient and safe retroviral and lentiviral vector systems for gene therapy. 相似文献
99.
Schaffer B Grogger W Kothleitner G Hofer F 《Analytical and bioanalytical chemistry》2008,390(6):1439-1445
In this work we show how energy-filtered imaging can be used to obtain spectrum images of electron energy-loss spectrometric
data. Focus is placed on improved energy resolution within these data sets. Using two multilayer samples (GaN/AlN and InP/InAs),
we demonstrate the advantages of spectrum-imaging and its extended mapping capabilities. Plasmon-ratio maps are used to quickly
create high-contrast material maps with high signal-to-noise ratio, ratio-contrast plots are used to gain optimum settings
for the ratio maps, and plasmon-position maps are used to map small shifts of the energy position of bulk plasmon peaks.
Figure Scheme of EELS SI and derived plasman-position map 相似文献
100.