Chromatographic columns and separation devices comprising a superficially porous material; and use thereof for supercritical fluid chromatography and other chromatography

Patent metadata

Field	Value
Publication number	US-11577179-B2
Application number	US-201414897584-A
Country	US
Kind code	B2
Filing date	Jun 10, 2014
Priority date	Jun 11, 2013
Publication date	Feb 14, 2023
Grant date	Feb 14, 2023

Abstract

The present invention provides methods for performing supercritical fluid chromatography comprising loading a sample to be separated by supercritical fluid chromatography onto a stationary phase comprising a spherical, monodisperse, core-shell particulate material comprising a nonporous core and one or more layers of a porous shell material surrounding the core, wherein the particles are sized less than 2 microns; and performing supercritical fluid chromatography to separate the sample.

First claim

What is claimed is:

1. A method for performing supercritical fluid chromatography comprising:
loading a sample comprising an analyte to be separated by supercritical fluid chromatography onto a stationary phase comprising a spherical, monodisperse, core-shell particulate material; and
performing supercritical fluid chromatography to separate said sample;
wherein a tailing factor associated with the stationary phase is about 0.80-2.0;
wherein the particulate material has a Formula 1:
[X](W) a (Q) b (T) c   Formula 1

where:
X is a superficially porous silica material, a superficially porous inorganic/organic hybrid material, or a superficially porous particulate material comprising a core having a pore volume of less than 0.10 cc/g and one or more layers of a porous shell material surrounding the core and wherein said particles are sized less than 2 microns;
W includes hydrogen and/or includes hydroxyl on the surface of X;
Q is bound directly to X and comprises a first hydrophilic, polar, ionizable, and/or charged functional group that chromatographically interacts with the analyte;
T is bound directly to X and comprises a second hydrophilic, polar, ionizable, and/or charged functional group that chromatographically interacts with the analyte;
wherein a is >0, b is >0, and c is >0, wherein a is >0, b=0 and c>0, or wherein a is >0, c=0 and b>0.

2. The method according to claim 1 , wherein the tailing factor associated with the stationary phase is about 0.85-1.60.

3. The method according to claim 2 , wherein the tailing factor associated with the stationary phase is about 0.90-1.30.

4. The method according to claim 3 , wherein the tailing factor associated with the stationary phase is about 0.95-1.20.

5. The method of claim 1 , wherein the core is a silica core.

6. The method of claim 5 , wherein the porous shell material is a porous inorganic/organic hybrid material.

7. The method of claim 5 , wherein the porous shell material is a porous silica material.

8. The method of claim 1 , wherein the core is an inorganic/organic hybrid core.

9. The method of claim 8 , wherein the porous shell material is a porous inorganic/organic hybrid material.

10. The method of claim 8 , wherein the porous shell material is a porous silica material.

11. The method of claim 1 , comprising more than one layer of porous shell material wherein each layer is independently selected from a porous inorganic/organic hybrid material and a porous silica.

12. The method of claim 1 , wherein the pores of the particulate material have an average diameter of about 25-600 A.

13. The method of claim 1 , wherein the pores of the particulate material have an average diameter of about 60-350 A.

14. The method of claim 1 , wherein the pores of the particulate material have an average diameter of about 80-300 A.

15. The method of claim 1 , wherein the pores of the particulate material have an average diameter of about 90-150 A.

16. The method of claim 1 , wherein the porous shell material has an increased average pore diameter near the surface of the porous shell material.

17. The method of claim 1 , wherein pores of the particulate material have an average pore volume of about 0.11-0.50 cm 3 /g.

18. The method of claim 1 , wherein pores of the particulate material have an average pore volume of about 0.09-0.45 cm 3 /g.

19. The method of claim 1 , wherein pores of the particulate material have an average pore volume of about 0.17-0.30 cm 3 /g.

20. The method of claim 1 , wherein the particulate material has a pore surface area between about 10 m 2 /g and 400 m 2 /g.

21. The method of claim 1 , wherein the particulate material has a pore surface area between about 15 m 2 /g and 300 m 2 /g.

22. The method of claim 1 , wherein the particulate material has a pore surface area between about 60 m 2 /g and 200 m 2 /g.

23. The method of claim 1 , wherein b>0 and wherein Q is represented by:

wherein:
n 1 an integer from 0-30;
n 2 an integer from 0-30;
n 3 =0 or 1, provided that when n 3 =0, n 1 is not 0;
each occurrence of R 1 , R 2 , R 3 and R 4 independently represents hydrogen, fluoro, methyl, ethyl, n-butyl, t-butyl, i-propyl, lower alkyl, a protected or deprotected alcohol, a zwitterion, or a group Z;
Z represents:
a) a surface attachment group having the formula
(B 1 ) x (R 5 ) y (R 6 ) z Si—wherein x is an integer from 1-3,
y is an integer from 0-2,
z is an integer from 0-2,
and x+y+z=3,
each occurrence of R 5 and R 6 independently represents methyl, ethyl, n-butyl, iso-butyl, tert-butyl, iso-propyl, thexyl, substituted or
unsubstituted aryl, cyclic alkyl, branched alkyl, lower alkyl, a protected or deprotected alcohol, or a zwitterion group, and
B 1 represents a siloxane bond; or
b) an attachment to a surface organofunctional hybrid group through a direct carbon-carbon bond formation or through a heteroatom, ester, ether, thioether, amine, amide, imide, urea, carbonate, carbamate, heterocycle, triazole, or urethane linkage; or c) an adsorbed, surface group that is not covalently attached to the surface of the material;
Y is an embedded polar functionality; and
A represents
i.) a hydrophilic terminal group;
ii.) hydrogen, fluoro, methyl, ethyl, n-butyl, t-butyl, propyl, lower alkyl, or group Z; or
iii.) a functionalizable group.

24. The method of claim 1 , wherein b>0 and wherein Q comprises one of the following structures:

Z represents:
a) a surface attachment group having the formula
(B 1 ) x (R 5 ) y (R 6 ) z Si—wherein x is an integer from 1-3,
y is an integer from 0-2,
z is an integer from 0-2,
and x+y+z=3,
each occurrence of R 5 and R 6 independently represents methyl, ethyl, n-butyl, iso-butyl, tert-butyl, iso-propyl, thexyl, substituted or
unsubstituted aryl, cyclic alkyl, branched alkyl, lower alkyl, a protected or deprotected alcohol, or a zwitterion group, and
B 1 represents a siloxane bond; or
b) an attachment to a surface organofunctional hybrid group through a direct carbon-carbon bond formation or through a heteroatom, ester, ether, thioether, amine, amide, imide, urea, carbonate, carbamate, heterocycle, triazole, or urethane linkage; or c) an adsorbed, surface group that is not covalently attached to the surface of the material.

25. The method of claim 1 , wherein c is >0 and wherein T is represented by:

wherein:
n′ an integer from 0-5;
n 2 an integer from 0-5;
n 3 =0 or 1, provided that when n 3 =0, n 1 is not 0;
each occurrence of R 1 , R 1 , R 3 and R 4 independently represents hydrogen, fluoro, methyl, ethyl, n-butyl, t-butyl, i-propyl, lower alkyl, a protected or deprotected alcohol, a zwitterion, or a g

Assignees

• Waters Technologies Corp

Inventors

• Wyndham Kevin D
• Fairchild Jacob N
• Iraneta Pamela C
• Shiner Stephen J
• Brousmiche Darryl W
• Walsh Daniel P

Classifications

• B01J20/286

  Phases chemically bonded to a substrate, e.g. to silica or to polymers · CPC title

• B01D15/08 Primary

  Selective adsorption, e.g. chromatography · CPC title

• B01D15/322

  Normal bonded phase · CPC title

• B01J20/28016

  Particle form · CPC title

• B01J20/28057

  Surface area, e.g. B.E.T specific surface area · CPC title