Non aqueous solvents or mixtures for dnp nmr spectroscopy, method to prepare said solvents or mixtures and use of said solvents or mixtures

Patent metadata

Field	Value
Publication number	US-2016195480-A1
Application number	US-201214125104-A
Country	US
Kind code	A1
Filing date	Jun 8, 2012
Priority date	Jun 10, 2011
Publication date	Jul 7, 2016
Grant date	—

Abstract

Non aqueous solvents or mixtures for DNP NMR spectroscopy, method to prepare said solvents or mixtures and use of said solvents or mixtures The present invention concerns a method to determine the efficiency of a solvent to impregnate a sample material for use in a dynamic nuclear polarization (DNP) nuclear magnetic resonance (NMR) experiments, characterized in that the method comprising: —selecting a non-aqueous solvent, —providing a polarizing agent that is soluble in the non-aqueous solvent, —dissolving the polarizing agent in the non-aqueous solvent, —impregnating or dissolving the sample material with the non-aqueous solvent containing the polarizing agent, —performing a solid state DNP NMR experiment on the impregnated sample material, —determining a DNP enhancement factor of the DNP NMR experiment.

First claim

1 - 15 . (canceled)

16 . A method of obtaining a DNP-enhanced NMR spectrum of a solid sample material, comprising:
using a mixture of a solvent and a polarizing agent; selecting a non-aqueous solvent; providing a polarizing agent that is soluble in the non-aqueous solvent; dissolving the polarizing agent in the non-aqueous solvent; impregnating the solid sample material with the non-aqueous solvent containing the polarizing agent; performing a solid state DNP NMR experiment on the impregnated solid sample material at a temperature below room temperature; and determining the DNP enhanced NMR spectrum, and, wherein the non-aqueous solvent contains at least one heteroatom as part of its chemical structure.

17 . The method of claim 16 , wherein the heteroatom is a halogen atom selected from the group consisting of a bromine atom, and a chlorine atom.

18 . The method of claim 16 , wherein the solid sample material is a solid at room temperature that contains mesopores on a scale between 1 nm and 10 nm, and wherein the non-aqueous solvent is selected such that its boiling point is high enough to prevent drying out of the impregnated sample material at room temperature.

19 . The method of claim 16 , wherein the non-aqueous solvent is selected such that its freezing point is high enough to allow simultaneous freezing with the solid sample material in the same temperature range below room temperature.

20 . The method of claim 16 , wherein the non-aqueous solvent is selected such that it provides efficient spin diffusion.

21 . The method of claim 16 , wherein the polarizing agent comprises biradicals formed by bTbK or TOTAPOL.

22 . The method of claim 16 , wherein the non-aqueous solvent comprises at least one of dichloromethane, chloroform, 1, 1, 2, 2 tetrachloroethane, 1, 1, 1 trichloroethane, trans-dichloroethane, 1, 2 dichlorobenzene, 1, 2 dichloroethane, 1, 2 dibromoethane, 1, 3 dibromobutane, and 1, 1, 2, 2 tetrabromoethane.

23 . The method of claim 16 , wherein the radical concentration of the polarizing agent in the non-aqueous solvent is in the range from 0.1 to 100 mM.

24 . The method of claim 17 , wherein the solid sample material is a solid at room temperature that contains mesopores on a scale between 1 nm and 10 nm,
wherein the non-aqueous solvent is selected such that its boiling point is high enough to prevent drying out of the impregnated sample material at room temperature, and wherein the non-aqueous solvent is selected such that its freezing point is high enough to allow simultaneous freezing with the solid sample material in the same temperature range below room temperature

25 . The method of claim 17 , wherein the polarizing agent comprises biradicals formed by bTbK or TOTAPOL.

26 . The method of claim 22 , wherein the polarizing agent comprises biradicals formed by bTbK or TOTAPOL.

27 . The method of claim 24 , wherein the polarizing agent comprises biradicals formed by bTbK or TOTAPOL.

28 . The method of claim 17 , wherein the non-aqueous solvent comprises at least one of dichloromethane, chloroform, 1, 1, 2, 2 tetrachloroethane, 1, 1, 1 trichloroethane, trans-dichloroethane, 1, 2 dichlorobenzene, 1, 2 dichloroethane, 1, 2 dibromoethane, 1, 3 dibromobutane, and 1, 1, 2, 2 tetrabromoethane.

29 . The method of claim 24 , wherein the non-aqueous solvent comprises at least one of dichloromethane, chloroform, 1, 1, 2, 2 tetrachloroethane, 1, 1, 1 trichloroethane, trans-dichloroethane, 1, 2 dichlorobenzene, 1, 2 dichloroethane, 1, 2 dibromoethane, 1, 3 dibromobutane, and 1, 1, 2, 2 tetrabromoethane.

30 . The method of claim 16 , wherein the heteroatom is a halogen atom selected from the group consisting of a bromine atom, and a chlorine atom,
wherein the solid sample material is a solid at room temperature that contains mesopores on a scale between 1 nm and 10 nm and wherein the non-aqueous solvent is selected such that its boiling point is high enough to prevent drying out of the impregnated sample material at room temperature, wherein the non-aqueous solvent is selected such that its freezing point is high enough to allow simultaneous freezing with the solid sample material in the same temperature range below room temperature, wherein the non-aqueous solvent is selected such that it provides efficient spin diffusion, wherein the non-aqueous solvent comprises at least one of dichloromethane, chloroform, 1, 1, 2, 2 tetrachloroethane, 1, 1, 1 trichloroethane, trans-dichloroethane, 1, 2 dichlorobenzene, 1, 2 dichloroethane, 1, 2 dibromoethane, 1, 3 dibromobutane, 1, 1, 2, 2 tetrabromoethane, wherein the polarizing agent comprises biradicals formed by bTbK or TOTAPOL, and wherein the radical concentration of the polarizing agent in the non-aqueous solvent is in the range from 0.1 to 100 mM.

31 . The method of claim 18 , wherein the boiling point is higher than 310K.

32 . The method of claim 19 , wherein the freezing point is higher than 150K.

33 . The method of claim 23 , wherein the radical concentration of the polarizing agent in the non-aqueous solvent is in the range from 5 to 20 mM.

34 . The method of claim 24 , wherein the boiling point is higher than 310K, and wherein the freezing point is higher than 150K.

35 . The method of claim 30 , wherein the boiling point is higher than 310K,
wherein the freezing point is higher than 150K, and wherein the radical concentration of the polarizing agent in the non-aqueous solvent is in the range from 5 to 20 mM

Assignees

• Maas Werner
• Rosay Mélanie
• Coperet Christophe
• Gajan David
• Emsley Lyndon
• Lelli Moreno
• Lesage Anne
• Rossini Aaron
• Zagdoun Alexandre
• Tordo Paul
• Ouari Olivier
• Bruker Biospin
• Eidgen Ssische Tech Hochschule Zurich
• Univ Aix Marseille
• Univ Claude Bernard Lyon
• Centre Nat Rech Scient
• Ecole Norm Superieure Lyon

Inventors

• Maas Werner
• Rosay Mélanie
• Coperet Christophe
• Gajan David
• Emsley Lyndon
• Lelli Moreno
• Lesage Anne
• Rossini Aaron
• Zagdoun Alexandre
• Tordo Paul
• Ouari Olivier

Classifications

• G01R33/46

  NMR spectroscopy · CPC title

• G01N24/12 Primary

  by using double resonance · CPC title

• G01R33/282

  Means specially adapted for hyperpolarisation or for hyperpolarised contrast agents, e.g. for the generation of hyperpolarised gases using optical pumping cells, for storing hyperpolarised contrast agents or for the determination of the polarisation of a hyperpolarised contrast agent · CPC title

• G01R33/62

  using double resonance (G01R33/24 takes precedence) · CPC title