Hybrid material for chromatographic separations comprising a superficially porous core and a surrounding material
The present invention provides novel chromatographic materials, e.g., for chromatographic separations, processes for their preparation and separations devices containing the chromatographic materials. The preparation of the inorganic/organic hybrid materials of the invention wherein a surrounding material is condensed on a superficially porous hybrid core material will allow for families of different hybrid packing materials to be prepared from a single core hybrid material. Differences in hydrophobicity, ion-exchange capacity, chemical stability, surface charge or silanol activity of the surrounding material may be used for unique chromatographic separations of small molecules, carbohydrates, antibodies, whole proteins, peptides, and/or DNA.
1. An inorganic/organic hybrid material comprising (a) a nonporous inorganic/organic hybrid surrounding material and (b) a superficially porous core that comprises a substantially nonporous core having a pore volume of less than 0.10 cc/g and one or more layers or porous inorganic/organic hybrid shell material surrounding the core, wherein the inorganic/organic hybrid shell material is different from the material of the superficially porous core and wherein the inorganic/organic hybrid surrounding material is condensed on the superficially porous core.
2. The inorganic/organic hybrid material of claim 1 , wherein the inorganic/organic surrounding material is derived from
condensation of one or more polymeric organofunctional metal precursors, and/or polymeric metal oxide precursors on a surface of the superficially porous core, or
application of partially condensed polymeric organofunctional metal precursors, a mixture of two or more polymeric organofunctional metal precursors, or a mixture of one or more polymeric organofunctional metal precursors with a polymeric metal oxide precursors on a surface of the superficially porous core.
3. The inorganic/organic hybrid material of claim 2 , wherein the inorganic portion of the inorganic/organic surrounding material is selected from the group consisting of alumina, silica, titania, cerium oxide, or zirconium oxide, and ceramic materials.
4. The inorganic/organic hybrid material of claim 1 , wherein the inorganic/organic surrounding material is derived from
condensation of one or more organofunctional silanes and/or tetraalkoxysilane on a surface of the superficially porous core, or
application of partially condensed organofunctional silane, a mixture of two or more organofunctional silanes, or a mixture of one or more organofunctional silanes with a tetraalkoxysilane on a surface of the superficially porous core.
5. The inorganic/organic hybrid material of claim 1 , wherein the inorganic/organic portion of the inorganic/organic surrounding material is selected from the group consisting of alumina, silica, titanium oxide, cerium oxide, zirconium oxide and ceramic materials.
6. The inorganic/organic hybrid material of claim 1 , wherein the inorganic/organic surrounding material comprises a material of formula I:
(SiO 2 ) d /[R 2 ((R) p (R 1 ) q SiO t ) m ; (I)
wherein,
R and R 1 are each independently C 1 -C 18 alkoxy, C 1 -C 18 alkyl, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 3 -C 18 cycloalkyl, C 1 -C 18 heterocycloalkyl, C 5 -C 18 aryl, C 5 -C 18 aryloxy, or C 1 -C 18 heteroaryl;
R 2 is C 1 -C 18 alkyl, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 3 -C 18 cycloalkyl, C 1 -C 18 heterocycloalkyl, C 5 -C 18 aryl, C 1 -C 18 heteroaryl; or absent; wherein each R 2 is attached to two or more silicon atoms;
p and q are each independently 0.0 to 3.0;
t is 0.5, 1.0, or 1.5;
d is 0 to about 30;
m is an integer from 1-20; wherein R, R 1 and R 2 are optionally substituted; provided that:
(
1
)
when
R
2
is
absent
,
m
=
1
and
t
=
(
4
-
(
p
+
q
)
)
2
,
when
0
<
p
+
q
<
3
;
and
(
2
)
when
R
2
is
present
,
m
=
2
-
20
and
t
=
(
3
-
(
p
+
q
)
)
2
,
when
p
+
q
<
2.
7. The inorganic/organic hybrid material of claim 1 , wherein the inorganic/organic surrounding material comprises a material of formula II:
(SiO 2 ) d /[(R) p (R 1 ) q SiO t ] (II);
wherein,
R and R 1 are each independently C 1 -C 18 alkoxy, C 1 -C 18 alkyl, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 3 -C 18 cycloalkyl, C 1 -C 18 heterocycloalkyl, C 5 -C 18 aryl, C 5 -C 18 aryloxy, or C 1 -C 18 heteroaryl;
d is 0 to about 30;
p and q are each independently 0.0 to 3.0, provided that when p+q=1 then t=1.5; when p+q=2 then t=1; or when p+q=3 then t=0.5.
8. The inorganic/organic hybrid material of claim 1 , wherein the inorganic/organic surrounding material comprises a material of formula III:
(SiO 2 ) d /[R 2 ((R 1 ) r SiO t ) m ] (III)
wherein
R 1 is C 1 -C 18 alkoxy, C 1 -C 18 alkyl, C 2 -C 18 alkynyl, C 3 -C 18 cycloalkyl, C 1 -C 18 heterocycloalkyl, C 5 -C 18 aryl, C 5 -C 18 aryloxy, or C 1 -C 18 heteroaryl;
R 2 is C 1 -C 18 alkyl, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 3 -C 18 cycloalkyl, C 1 -C 18 heterocycloalkyl, C 5 -C 18 aryl, C 1 -C 18 heteroaryl; or absent; wherein each R 2 is attached to two or more silicon atoms;
d is 0 to about 30;
r is 0, 1 or 2, provided that when r=0 then t=1.5; or when r=1 then t=1; or when r=2 then t=0.5; and
m is an integer from 1-20.
9. The inorganic/organic hybrid material of claim 1 , wherein the inorganic/organic hybrid shell has formula I:
(SiO 2 ) d /[R 2 ((R) p (R 1 ) q SiO t ) m ; (I)
wherein,
R and R 1 are each independently C 1 -C 18 alkoxy, C 1 -C 18 alkyl, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 3 -C 18 cycloalkyl, C 1 -C 18 heterocycloalkyl, C 5 -C 18 aryl, C 5 -C 18 aryloxy, or C 1 -C 18 heteroaryl;
R 2 is C 1 -C 18 alkyl, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 3 -C 18 cycloalkyl, C 1 -C 18 heterocycloalkyl, C 5 -C 18 aryl, C 1 -C 18 heteroaryl; or absent; wherein each R 2 is attached to two or more silicon atoms;
p and q are each independently 0.0 to 3.0;
tis 0.5, 1.0, or 1.5;
d is 0 to about 30;
m is an integer from 1-20; wherein R, R 1 and R 2 are optionally substituted;
provided that:
(
1
)
when
R
2
is
absent
,
m
=
1
and
t
=
(
4
-
(
p
+
q
)
)
2
,
when
0
<
p
+
q
<
3
;
and
(
2
)
when
R
2
is
present
,
m
=
2
-
20
and
t
=
(
3
-
(
p
+
q
)
)
2
,
when
p
+
q
<
2
.
10. The inorganic/organic hybrid material of claim 1 , wherein the inorganic/organic hybrid shell has formula II:
(SiO 2 ) d /[(R) p (R 1 ) q SiO t ] (II);
wherein,
R and R 1 are each independently C 1 -C 18 alkoxy, C 1 -C 18 alkyl, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 3 -C 18 cycloalkyl, C 1 -C 18 heterocycloalkyl, C 5 -C 18 aryl, C 5 -C 18 aryloxy, or C 1 -C 18 heteroaryl;
d is 0 to about 30;
p and q are each independently 0.0 to 3.0, provided that when p+q=1 then t=1.5; when p+q=2 then t=1; or when p+q=3 then t=0.5.
11. The inorganic/organic hybrid material of claim 1 , wherein the inorganic/organic hybrid shell has formula III:
(SiO 2 ) d /[R 2 ((R 1 ) n SiO t ) m ] (III)
wherein,
R 1 is C 1 -C 18 alkoxy, C 1 -C 18 alkyl, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 3 -C 18 cycloalkyl, C 1 -C 18 heterocycloalkyl, C 5 -C 18 aryl, C 5 -C 18 aryloxy, or C 1 -C 18 heteroaryl;
R 2 is C 1 -C 18 alkyl, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 3 -C 18 cycloalkyl, C 1 -C 18 heterocycloalkyl, C 5 -C 18 aryl, C 1 -C 18 heteroaryl; or absent; wherein each R 2 is attached to two or more silicon atoms;
d is 0 to about 30;
r is 0, 1 or 2, provided that when r=0 then t=1.5; or when r=1 then t=1; or when r=2 then t=0.5; and
m is an integer from 1-20.
12. The inorganic/organic hybrid material of claim 1 , wherein the superficially porous core is a particle.
13. The inorganic/organic hybrid material of claim 1 , wherein the inorganic/organic hybrid material is hydrolytically stable at a pH of about 1 to about 14.
14. The inorganic/organic hybrid material of claim 1 , wherein said inorganic/organic hybrid material has been surface modified by coating with a polymer.
15. The inorganic/organic hybrid material of claim 1 , wherein said inorganic/organic hybrid material has been surface modified by a combination of organic group and silanol group modification.
16. The inorganic/organic hybrid material of claim 1 , wherein said inorganic/organic hybrid material has been surface modified by a combination of organic group modification and coating with a polymer.
17. The inorganic/organic hybrid material of claim 1 , wherein said inorganic/organic hybrid material has been surface modified by a combination of silanol group modification and coating with a polymer.
18. The inorganic/organic hybrid material of claim 1 , wherein said inorganic/organic hybrid material has been surface modified via formation of an organic covalent bond between an organic group of the inorganic/organic hybrid material and a modifying reagent.
19. The inorganic/organic hybrid material of claim 1 , wherein said inorganic/organic hybrid material has been surface modified by a combination of organic group modification, silanol group modification and coating with a polymer.
20. The inorganic/organic hybrid material of claim 1 , wherein said inorganic/organic hybrid material has been surface modified by silanol modification.
21. The inorganic/organic hybrid material of claim 1 , wherein the superficially porous core is derived from condensation of one or more organofunctional silanes selected from the following:
wherein R and R 1 are each independently C 1 -C 18 alkoxy, C 1 -C 18 alkyl, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 3 -C 18 cycloalkyl, C 1 -C 18 heterocycloalkyl, C 5 -C 18 aryl, C 5 -C 18 aryloxy, or C 1 -C 18 heteroaryl and
wherein R 2 is C 1 -C 18 alkyl, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 3 -C 18 cycloalkyl, C 1 -C 18 heterocycloalkyl, C 5 -C 18 aryl, C 1 -C 18 heteroaryl; or absent; wherein each R 2 is attached to two or more silicon atoms; wherein n is 1-8.