AI Article Synopsis
- A new water-soluble Rh(I)-based catalyst for parahydrogen induced polarization (PHIP) has been developed, featuring the inexpensive ligand tris(hydroxymethyl)phosphine (THP).
- This monodentate catalyst is more resistant to oxidation from air compared to more complex bidentate counterparts and shows competitive performance.
- The catalyst achieved a noteworthy 12% (13)C polarization for the product 2-hydroxyethyl 1-(13)C-propionate-d(2,3,3) in water, indicating effective hydrogenation even with oxidized THP present.
Article Abstract
Reported here is a water soluble Rh(I)-based catalyst for performing parahydrogen induced polarization (PHIP). The [Rh(I)(norbornadiene)(THP)(2)](+)[BF(4)](-) catalyst utilizes the monodentate phosphine ligand tris(hydroxymethyl)phosphine (THP). The monodentate PHIP catalyst is less susceptible to oxygenation by air and THP ligand and is significantly less expensive than bidentate water-soluble PHIP ligands. In situ PHIP detection with this monodentate Rh(I) based catalyst in water yielded 12% (13)C polarization for the parahydrogen addition product, 2-hydroxyethyl 1-(13)C-propionate-d(2,3,3) (HEP), with a (13)C T(1) relaxation of 108 seconds at 0.0475 T. PHIP polarization yields were high, reflecting efficient hydrogenation even under conditions of high content of the oxidized phosphine form of the THP ligand.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC3515067 | PMC |
| http://dx.doi.org/10.1021/jz301389r | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Tailoring rhodium-based metal-organic layers for parahydrogen-induced polarization: achieving 20% polarization of H in liquid phase.
Natl Sci Rev
January 2025
State Key Laboratory of Physical Chemistry of Solid Surfaces, School of Electronic Science and Engineering, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
Heterogeneous catalysts for parahydrogen-induced polarization (HET-PHIP) would be useful for producing highly sensitive contrasting agents for magnetic resonance imaging (MRI) in the liquid phase, as they can be removed by simple filtration. Although homogeneous hydrogenation catalysts are highly efficient for PHIP, their sensitivity decreases when anchored on porous supports due to slow substrate diffusion to the active sites and rapid depolarization within the channels. To address this challenge, we explored 2D metal-organic layers (MOLs) as supports for active Rh complexes with diverse phosphine ligands and tunable hydrogenation activities, taking advantage of the accessible active sites and chemical adaptability of the MOLs.
View Article and Find Full Text PDFHigh H Solubility of Perfluorocarbon Solvents and Their Use in Reversible Polarization Transfer from -Hydrogen.
J Phys Chem Lett
January 2025
Centre for Hyperpolarization in Magnetic Resonance, University of York, Heslington YO10 5NY, United Kingdom.
This research uses perfluorocarbons (PFCs) as effective alternatives to traditional toxic solvents in reversible -hydrogen-induced polarization (PHIP) for NMR signal enhancement. Hydrogen solubility in PFCs is shown here to be an order of magnitude higher than in typical organic solvents by determination of Henry's constants. We demonstrate how this high H solubility enables the PFCs to deliver substantial polarization transfer from -hydrogen, achieving up to 2400-fold signal gains for H NMR detection and 67,000-fold (22% polarization) for N NMR detection at 9.
View Article and Find Full Text PDFEnhancing Sensitivity of Nuclear Magnetic Resonance in Biomolecules: Parahydrogen-Induced Hyperpolarization in Synthetic Disulfide-Rich Miniproteins.
J Am Chem Soc
December 2024
Eduard-Zintl-Institut für Anorganische und Physikalische Chemie, Technische Universität Darmstadt, Peter-Grünberg-Straße 8, 64287 Darmstadt, Germany.
Hyperpolarization of small peptides by parahydrogen-induced polarization (PHIP) to increase the sensitivity of nuclear magnetic resonance (NMR) techniques is well established, while its application to larger biopolymers is still a mainly unexplored area. A particular challenge is the presence of folding-essential disulfide bridges. They tend to form metal complexes, thus hampering catalytic hydrogenation, a prerequisite for PHIP.
View Article and Find Full Text PDFParahydrogen Polarization in Reverse Micelles and Application to Sensing of Protein-Ligand Binding.
J Am Chem Soc
December 2024
Chemistry Department, Texas A&M University, 3255 TAMU, College Station, Texas 77843, United States.
A medium containing reverse micelles supports non-hydrogenative parahydrogen induced polarization (nhPHIP) in the organic phase while solubilizing a protein in the aqueous phase. Strongly enhanced NMR signals from iridium hydride complexes report on a ligand, 4-amino-2-benzylaminopyrimidine, which crosses the phase boundary and interacts with the thiaminase protein TenA. The calculation of binding equilibria reveals a of 39.
View Article and Find Full Text PDFHyperpolarised benchtop NMR spectroscopy for analytical applications.
Prog Nucl Magn Reson Spectrosc
October 2024
Department of Chemistry, University of York, York, YO10 5DD, UK. Electronic address:
Benchtop NMR spectrometers, with moderate magnetic field strengths (B=1-2.4T) and sub-ppm chemical shift resolution, are an affordable and portable alternative to standard laboratory NMR (B≥7T). However, in moving to lower magnetic field instruments, sensitivity and chemical shift resolution are significantly reduced.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!