Solid state NMR spectroscopy/imaging in situ measuring devices and methods for calibration and determining one or more quantitative properties of a target sample

Patent metadata

Field	Value
Publication number	US-10067079-B2
Application number	US-201514941372-A
Country	US
Kind code	B2
Filing date	Nov 13, 2015
Priority date	Oct 15, 2014
Publication date	Sep 4, 2018
Grant date	Sep 4, 2018

Abstract

In situ measuring devices, methods of making the same, and methods of using the same are provided herein. The in situ measuring devices can include a capillary tube having a reference material sealed inside the capillary tube, where the capillary tube is positioned inside of a solid state or MAS NMR rotor. A target sample can also be positioned in the interior of the solid state or MAS NMR rotor but is sequestered from the reference material by a capillary tube wall. The in situ measuring devices can be used in solid state MAS NMR spectroscopy to quantify one or more parameters of a target sample, such as the quantity of a sample, chemical identity of a sample, or temperature of a sample.

First claim

What is claimed is:

1. A method for performing one or more quantitative measurements of a target sample using solid state Magic Angle Spinning (MAS) Nuclear Magnetic Resonance (NMR) spectroscopy, the method comprising:
providing an in situ measuring device, the in situ measuring device comprising a solid state MAS NMR rotor and at least one sealed capillary tube positioned inside the solid state MAS NMR rotor, the at least one sealed capillary tube having a reference material sealed inside the at least one capillary tube between first and second fused glass ends of the at least one sealed capillary tube, wherein a target sample is positioned on the inside of the solid state MAS NMR rotor, and wherein a first portion of the target sample is in contact with an inner surface of the solid state MAS NMR rotor and a second portion of the target sample is in contact with an outer surface of the at least one sealed capillary tube;
obtaining MAS NMR spectra of the target sample and the reference material; and
determining one or more quantitative properties of the target sample, the one or more quantitative properties comprising one or more of a quantity of the target sample, a chemical identity of the target sample, or a temperature of the target sample.

2. The method of claim 1 , wherein the reference material comprises one or more of ethylene glycol, methanol, ethanol, water, or mixtures thereof.

3. The method of claim 1 , wherein the at least one sealed capillary tube comprises a plurality of sealed capillary tubes, wherein each of the plurality of sealed capillary tubes are positioned inside the solid state MAS NMR rotor.

4. The method of claim 3 , wherein each of the plurality of sealed capillary tubes has the same reference material sealed inside.

5. The method of claim 1 , wherein the obtaining MAS NMR spectra of the target sample and the reference material comprises simultaneously obtaining the MAS NMR spectra of the target sample and the reference material.

6. The method of claim 1 , wherein the one or more quantitative properties comprises the chemical identity of the target sample.

7. The method of claim 1 , wherein the one or more quantitative properties comprises the quantity of the target sample.

8. The method of claim 1 , wherein the one or more quantitative properties comprises the temperature of the target sample.

9. The method of claim 1 , wherein the at least one sealed capillary tube has an outer diameter less than 600 micrometers.

10. A method for performing one or more quantitative measurements of a target sample using solid state Magic Angle Spinning (MAS) Nuclear Magnetic Resonance (NMR) spectroscopy, the method comprising:
providing an in situ measuring device, the in situ measuring device comprising a solid state MAS NMR rotor and at least one sealed capillary tube positioned inside the solid state MAS NMR rotor, the at least one sealed capillary tube having a reference material sealed inside the at least one capillary tube between first and second fused glass ends of the at least one sealed capillary tube, wherein a target sample is positioned on the inside of the solid state MAS NMR rotor, and wherein a first portion of the target sample is in contact with an inner surface of the solid state MAS NMR rotor and a second portion of the target sample is in contact with an outer surface of the at least one sealed capillary tube;
inserting the in situ measuring device inside a probe of a solid state MAS NMR instrument,
while the in situ measuring device is positioned inside a probe of a solid state MAS NMR instrument, obtaining MAS NMR spectra of the target sample and the reference material, wherein at least one MAS NMR spectra peak associated with the reference material is spaced apart from at least one MAS NMR spectra peak associated with the target material; and
determining one or more of a quantity of the target sample or a chemical identity of the target sample based on the MAS NMR spectra of the target sample and the reference material.

11. The method of claim 10 , wherein the reference material comprises one or more of ethylene glycol, methanol, ethanol, water, or mixtures thereof.

12. The method of claim 10 , wherein the obtaining MAS NMR spectra of the target sample and the reference material comprises recording the solid state MAS NMR spectra using a Bloch decay pulse sequence.

13. The method of claim 10 , wherein the at least one sealed capillary tube has an outer diameter less than 600 micrometers.

14. A method for forming an in situ measuring device for solid state Magic Angle Spinning (MAS) Nuclear Magnetic Resonance (NMR) spectroscopy, the method comprising:
providing at least one capillary tube;
adding at least one reference material to an inside cavity of the at least one capillary tube;
sealing the at least one capillary tube by fusing glass at a first end and a second end to form at least one sealed capillary tube having the at least one reference material sealed inside;
providing a solid state MAS NMR rotor, the solid state MAS NMR rotor configured to house a target sample;
positioning the at least one sealed capillary tube inside the solid state MAS NMR rotor; and
adding at least one target material to the interior of the solid state MAS NMR rotor such that at least a portion of the target material is in contact with an inner surface of the solid state MAS NMR rotor and at least another portion of the target material is in contact with an outer surface of the at least one sealed capillary tube.

15. The method of claim 14 , wherein the sealing the at least one capillary tube is performed using a micro torch.

16. The method of claim 14 , wherein the at least one capillary tube is coupled to a foundation member at one end of the at least capillary tube.

17. The method of claim 16 , wherein the positioning the at least one sealed capillary tube inside the solid state MAS NMR rotor comprises positioning the foundation member adjacent to a bottom inner surface of the solid state MAS NMR rotor.

18. The method of claim 14 , wherein the at least one sealed capillary tube is positioned in the center of the solid state MAS NMR rotor.

19. The method of claim 14 , wherein the at least one sealed capillary tube comprises a plurality of sealed capillary tubes.

20. The method of claim 14 , wherein the at least one sealed capillary tube has an outer diameter that is less than 600 micrometers.

Assignees

• Univ Missouri

Inventors

• Chi Lingyu
• Huang Ming
• Gerald Ii Rex E
• Woelk Klaus

Classifications

• G01R33/307

  specially adapted for moving the sample relative to the MR system, e.g. spinning mechanisms, flow cells or means for positioning the sample inside a spectrometer · CPC title

• G01R33/31

  Temperature control thereof · CPC title

• G01N24/08 Primary

  by using nuclear magnetic resonance (G01N24/12 takes precedence) · CPC title

• G01R33/4804

  Spatially selective measurement of temperature or pH · CPC title

• G01R33/0052

  Manufacturing aspects; Manufacturing of single devices, i.e. of semiconductor magnetic sensor chips (devices based on galvano-magnetic effect or the like H10N50/85) · CPC title