Use of vapor deposition coated flow paths for improved chromatography of metal interacting analytes

Patent metadata

Field	Value
Publication number	US-11709155-B2
Application number	US-201816133089-A
Country	US
Kind code	B2
Filing date	Sep 17, 2018
Priority date	Sep 18, 2017
Publication date	Jul 25, 2023
Grant date	Jul 25, 2023

Abstract

A device for separating analytes is disclosed. The device has a sample injector, sample injection needle, sample reservoir container in communication with the sample injector, chromatography column downstream of the sample injector, and fluid conduits connecting the sample injector and the column. The interior surfaces of the fluid conduits, sample injector, sample reservoir container, and column form a flow path having wetted surfaces. A portion of the wetted surfaces of the flow path are coated with an alkylsilyl coating that is inert to at least one of the analytes. The alkylsilyl coating has the Formula I:R1, R2, R3, R4, R5, and R6 are each independently selected from (C1-C6)alkoxy, —NH(C1-C6)alkyl, —N((C1-C6)alkyl)2, OH, ORA, and halo. RA represents a point of attachment to the interior surfaces of the fluidic system. At least one of R1, R2, R3, R4, R5, and R6 is ORA. X is (C1-C20)alkyl, —O[(CH2)2O]1-20—, —(C1-C10)[NH(CO)NH(C1-C10)]1-20—, or —(C1-C10)[alkylphenyl(C1-C10)alkyl]1-20-.

First claim

What is claimed is:

1. A chromatographic device for separating analytes in a sample comprising:
a sample injector having a sample injection needle for injecting the sample into a mobile phase;
a sample reservoir container in fluid communication with the sample injector;
a chromatography column downstream of the sample injector, the chromatography column having fluid connectors and frits; and
fluid conduits connecting the sample injector and the chromatography column;
wherein interior surfaces of the fluid conduits, sample injector, sample reservoir container, and chromatography column, including the fluid connectors and frits, form a fluidic flow path having wetted surfaces; and
wherein at least a portion of the wetted surfaces of the fluidic flow path are metallic and are coated with an alkylsilyl coating, wherein the alkylsilyl coating is inert to at least one of the analytes in the sample, the alkylsilyl coating having the Formula I:

wherein
at least one of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 is OR A ;
when R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are not OR A , then R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from (C 1 -C 6 )alkoxy, —NH(C 1 -C 6 )alkyl, —N((C 1 -C 6 )alkyl) 2 , OH, and halo;
R A represents a point of attachment to the interior surfaces of the fluidic system; and

X is (C 1 -C 20 )alkyl, —O[(CH 2 ) 2 O] 1-20 —, —(C 1 -C 10 )[NH(CO)NH(C 1 -C 10 )] 1-20 —, or —(C 1 -C 10 )[alkylphenyl(C 1 -C 10 )alkyl] 1-20 —.

2. The chromatographic device of claim 1 , wherein the alkylsilyl coating has a contact angle of at least 15°.

3. The chromatographic device of claim 1 , wherein the alkylsilyl coating has a contact angle less than or equal to 30°.

4. The chromatographic device of claim 1 further comprising a detector downstream of the chromatography column and wherein the fluidic flow path further comprises the detector.

5. The chromatographic device of claim 4 , wherein the detector is a mass spectrometer and the fluidic flow path includes wetted surfaces of an electrospray needle.

6. The chromatographic device of claim 1 , wherein the fluidic flow path has a length to diameter ratio of at least 20.

7. The chromatographic device of claim 1 , wherein the alkylsilyl coating has a thickness of at least 100 Å.

8. The chromatographic device of claim 1 , wherein X is (C2-C10)alkyl.

9. The chromatographic device of claim 1 , wherein X is ethyl.

10. The chromatographic device of claim 1 , wherein R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each methoxy or chloro.

11. The chromatographic device of claim 1 , wherein the alkylsilyl coating of Formula I is bis(trichlorosilyl)ethane or bis(trimethoxysilyl)ethane.

12. The chromatographic device of claim 1 , further comprising a second alkylsilyl coating in direct contact with the alkylsilyl coating of Formula I, the second alkylsilyl coating having the Formula II:

wherein
R 7 , R 8 , and R 9 are each independently selected from —NH(C 1 -C 6 )alkyl, —N[(C 1 -C 6 )alkyl] 2 , (C 1 -C 6 )alkoxy, (C 1 -C 6 )alkyl, (C 1 -C 6 )alkenyl, OH, and halo;
R 10 is selected from (C 1 -C 6 )alkyl, —OR B , —[O(C 1 -C 3 )alkyl] 1-10 O(C 1 -C 6 )alkyl, —[O(C 1 -C 3 )alkyl] 1-10 OH and phenyl, wherein said (C 1 -C 6 )alkyl is optionally substituted with one or more halo and wherein said phenyl is optionally substituted with one or more groups selected from (C 1 -C 3 )alkyl, hydroxyl, fluorine, chlorine, bromine, cyano, —C(O)NH 2 , and carboxyl;
R B is —(C 1 -C 3 )alkyloxirane, —(C 1 -C 3 )alkyl-3,4-epoxycyclohexyl, or —(C 1 -C 4 )alkylOH;
the hashed bond to R 10 represents an optional additional covalent bond between R 10 and the carbon bridging the silyl group to form an alkene, provided y is not 0; and
y is an integer from 0 to 20.

13. The chromatographic device of claim 12 , wherein y is an integer from 2 to 9.

14. The chromatographic device of claim 12 , wherein y is 9, R 10 is methyl, and R 7 , R 8 , and R 9 are each ethoxy or chloro.

15. The chromatographic device of claim 12 , wherein the alkylsilyl coating of Formula II is (3-glycidyloxypropyl)trimethoxysilane, n-decyltrichlorosilane, trimethylchlorosilane, trimethyldimethyaminosilane, methoxy-polyethyleneoxy(1-10) propyl trichlorosilane, or methoxy-polyethyleneoxy(1-10) propyl trimethoxysilane.

16. The chromatographic device of claim 12 , wherein the alkylsilyl coating of Formula II is (3-glycidyloxypropyl)trimethoxysilane followed by hydrolysis.

17. The chromatographic device of claim 12 , wherein the alkylsilyl coating of Formula I and II provides a desired contact angle of about 0° to about 105°.

18. The chromatographic device of claim 12 , wherein the alkylsilyl coating of Formula I is bis(trichlorosilyl)ethane or bis(trimethoxysilyl)ethane and the alkylsilyl coating of Formula II is (3-glycidyloxypropyl)trimethoxysilane.

19. The chromatographic device of claim 12 , wherein the alkylsilyl coating of Formula I is bis(trichlorosilyl)ethane or bis(trimethoxysilyl)ethane and the alkylsilyl coating of Formula II is (3-glycidyloxypropyl)trimethoxysilane followed by hydrolysis.

20. The chromatographic device of claim 12 , wherein the alkylsilyl coating of Formula I is bis(trichlorosilyl)ethane or bis(trimethoxysilyl)ethane and the alkylsilyl coating of Formula II is n-decyltrichlorosilane.

21. The chromatographic device of claim 12 , wherein the alkylsilyl coating of Formula I is bis(trichlorosilyl)ethane or bis(trimethoxysilyl)ethane and the alkylsilyl coating of Formula II is trimethylchlorosilane or trimethyldimethylaminosilane [[trimethyldimethyaminosilane]].

22. The chromatographic device of claim 12 , wherein the alkylsilyl coating of Formula I is bis(trichlorosilyl)ethane or bis(trimethoxysilyl)ethane and the alkylsilyl coating of Formula II is methoxy-polyethyleneoxy(3)silane.

23. The chromatographic device of claim 1 , further comprising an alkylsilyl coating having the Formula III in direct contact with the alkylsilyl coating of Formula I,

wherein
R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 are each independently selected from (C 1 -C 6 )alkoxy, —NH(C 1 -C 6 )alkyl, —N((C 1 -C 6 )alkyl) 2 , OH, and halo; and

Z is (C 1 -C 20 )alkyl, —O[(CH 2 ) 2 O] 1-20 —, —(C 1 -C 10 )[NH(CO)NH(C 1 -C 10 )] 1-20 —, or —(C 1 -C 10 )[alkylphenyl(C 1 -C 10 )alkyl] 1-20 —.

24. The chromatographic device of claim 23 , wherein the alkylsilyl coating of Formula III is bis(trichlorosilyl)ethane or bis(trimethoxysilyl)ethane.

25. The chromatographic device of claim 23 , wherein the alkylsilyl coating of Formula I is bis(trichlorosilyl)ethane or bis(trimethoxysilyl)ethane and the alkylsilyl coating of Formula III is bis(trichlorosilyl)ethane or bis(trimethoxysilyl)ethane.

26. The chromatographic device of claim 25 , wherein the alkylsilyl coatings of Formula I and Formula III have a total thickness of about 400 Å.

Assignees

• Waters Technologies Corp

Inventors

• Lauber Matthew A
• Delano Mathew H
• Mccall Scott A
• Belanger Jonathan L
• Dourdeville Theodore A
• Smith Kerri M
• Rainville Paul D
• Shah Dimple D
• Shiner Stephen J
• Doneanu Catalin
• Donegan Michael

Classifications

• G01N30/56 Primary

  Packing methods or coating methods · CPC title

• B01J20/291

  Gel sorbents · CPC title

• B01J20/3272

  Polymers obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds · CPC title

• B05D1/60

  Deposition of organic layers from vapour phase (vapour phase deposition in general C23C14/00, C23C16/00) · CPC title

• C23C14/046

  Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates · CPC title