Polar silanes and their use on silica supports

Details Polar silanes and their use on silica supports Polar silanes and their use on silica supports

2002-03-05

2003-11-11

Therkorn, Ernest G. (Department: 1723)

Liquid purification or separation

With means to add treating material

Chromatography

C210S502100, C210S635000, C210S656000, C502S401000

Reexamination Certificate

active

06645378

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to new stationary phases and their use in HPLC (High Performance Liquid Chromatography), LC/MS and other preparative and analytical methods. More particularly, this invention relates to new silanes, their immobilization on silica supports and use of the modified silica supports as stationary phases in liquid chromatography (LC), LC/MS and other preparative and analytical methods.
BACKGROUND OF THE INVENTION
HPLC is widely used to separate analytes in liquid samples. The sample is injected in an eluent into a chromatography column. The sample components are separated by one or more mechanisms including sorption, size exclusion, ion exchange or other interactions with the chromatography packing. The sample components are then detected by any conventional detector, e.g., UV, fluorescence or conductivity.
Silica-based RP (reverse phase) packing materials are commonly used in chromatography columns. They contain unreacted silanol groups on the silica surfaces. Residual silanol sites can interact with polar analytes, especially with basic compounds via ion exchange, hydrogen bonding and dipole-dipole mechanisms. These interactions can create problems ranging from increased retention to excessive tailing and irreversible adsorption of the sample. These undesirable effects can be minimized by using ultra pure silica and maximizing the surface coverage with hydrophobic ligands and endcapping reagents. However, highly aqueous mobile phases are often required to conduct separation of hydrophilic analytes by RP HPLC. Conventional RP C18 columns show a reversible loss of retention when operated under these conditions. The rate and degree of retention loss can vary greatly among different columns. A common explanation for this effect is that the hydrophobic alkyl chains are not wettable and appear to fold down on the silica surface to avoid the exposure to hydrophilic media. In this folded or matted-down state, the alkyl chains have reduced surface area for hydrophobic interaction with the solutes resulting in loss of retention. Reid, T. S.; Henry, R. A.,
American Laboratory
24-28 (July 1999).
In order to achieve the compatibility of RP C18 HPLC columns with highly aqueous mobile phases and to improve the peak shape of basic analytes, polar-embedded phases have been suggested. Majors, R. E.,
LC
-
GC
19:272-288 (2001). These phases are primarily hydrophobic but have hydrophilic groups incorporated near the silica surface. A benefit of this modification is that the polar-embedded phases exhibit typical reversed-phase behavior with water-organic solvent mixtures and can function well in highly aqueous environment with little or even no organic modifier present. The hydrophilic moieties also can impart different selectivity and retention characteristics compared to conventional reversed-phase materials. Polar-embedded phases have improved tailing characteristics for basic analytes due to shielding effect of the incorporated polar groups on residual silanols. Polar groups mask undesirable silanol activity and prevent hydrophilic analytes from being retained via interaction with underivatized silica surface.
In the early 1990's, conventional C18 and C8 silica stationary phases continued yielding large tailing factors for basic analytes. At that time, several research groups reported a novel type of bonded phases in which a polar functional group was embedded into the alkyl chains. These materials were found to reduce silanol interactions with basic analytes. The most commonly used polar groups were amide, urea, ether and carbamate functionalities.
Early reported materials were prepared by a two-step surface modification. Feibush, B. EP-A-0386926 (1990). In step one, the silica support was bonded with an aminopropyl silane In step two, the amino groups reacted with an acid chloride to form amide linkages. This first generation methodology suffers from poor surface reproducibly over two successive reactions. Functionalized surface has a mixture of derivatized and underivatized amino groups. Therefore, the resulting phases exhibited undesirable ion exchange interactions due to the presence of unreacted basic sites.
Later, materials were prepared by one-step surface modification, where polar functional groups were built into a silane molecule. Neue, U. D.; Niederländer, C. L.; Perterson, J. S., EP-B-0579102 (1993). A single surface reaction with silane yields only one ligand structure with no anion exchange functionality being present.
SUMMARY OF THE INVENTION
One aspect of the invention relates to a modified silica support having a polar phase bound to its surface and suitable for use for chromatographic separations. The modified silica support has the following formula:
wherein,
m=0-20; n=0-20; p=1-50;
X is sulfonyl, carbonyl, carbamoyl, or oxycarbonyl;
R
1
=H, alkyl, substituted alkyl, aryl or substituted aryl groups;
R
2
=alkyl, substituted alkyl, aryl or substituted aryl groups; and
R
3
and R
4
are alkyl, aryl, hydroxyl, or alkoxyl groups or groups including oxygen atoms cross-linked to silicon atoms.
Another aspect of the invention relates to polar silanes useful as an intermediate in forming the polar phase of the modified silica support. The polar silane has the following formula:
wherein,
m=0-20; n=0-20; p=0-50;
X is a sulfonyl, carbonyl, carbamoyl, or oxycarbonyl, provided that p=at least 1 where X is a carbonyl, carbamoyl or oxycarbonyl;
R
1
=H, alkyl, substituted alkyl, aryl or substituted aryl groups;
R
2
=alkyl, substituted alkyl, aryl or substituted aryl groups;
R
3
, R
4
and R
5
are alkyl, aryl or reactive leaving groups and at least one of R
3
, R
4
or R
5
is a leaving group (such as an alkoxyl, halide, hydroxyl or amino group).


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Reid, T.S. and Henry, R.A., American Laboratory 24-28 (Jul. 1999).
Majors, R.E., New Chromatography Columns and Accessories at the 2001 Pittsburgh Conference, Part 1, LCGC 19:272-288 (Mar. 2001).
Waters Corporation, “A Review of Waters' Bonded Phase Shield Technology and Its Use in High Performance Liquid Chromatography,” (Apr. 2000).

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