Hybrid inorganic/organic materials having novel surface modification; process for the preparation of inorganic/organic hybrid materials; and use of said particles for chromatographic separations
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 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, 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 an inorganic/organic hybrid surrounding material and an inorganic/organic hybrid core;
wherein the inorganic/organic hybrid surrounding material comprises a material of a formula selected from the group consisting 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, wherein each R 2 is attached to two or more silicon atoms;
p and q are each independently 0.0 to 2.0;
t is 0.5, 1.0, or 1.5;
d is 0 to about 30;
m is an integer from 2-20;
t
=
(
3
-
(
p
+
q
)
)
2
and p+q≤2;
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 p+q=1, 2, or 3;
wherein when p+q=1, then t=1.5; when p+q=2, then t=1; and when p+q=3, then t=0.5;
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 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; wherein each R 2 is attached to two or more silicon atoms;
d is 0 to about 30;
r is 0, 1 or 2, wherein 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;
formula IV:
(A) x (B) y (C) z (IV),
wherein the order of repeat units A, B, and C may be random, block, or a combination of random and block;
A is an organic repeat unit which is covalently bonded to one or more repeat units A or B via an organic bond;
B is an organosiloxane repeat unit which is bonded to one or more repeat units B or C via an inorganic siloxane bond and which may be further bonded to one or more repeat units A or B via an organic bond;
C is an inorganic repeat unit which is bonded to one or more repeat units B or C via an inorganic bond; and
x and y are positive numbers and z is a non negative number, wherein
when z=0, then 0.002≤x/y≤210, and when z≠0, then 0.0003≤y/z≤500 and 0.002≤x/(y+z)≤210; and
formula V:
(A) x (B) y (B*) y *(C) z (V),
wherein the order of repeat units A, B, B*, and C may be random, block, or a combination of random and block;
A is an organic repeat unit which is covalently bonded to one or more repeat units A or B via an organic bond;
B is an organosiloxane repeat units which is bonded to one or more repeat units B or B* or C via an inorganic siloxane bond and which may be further bonded to one or more repeat units A or B via an organic bond;
B* is an organosiloxane repeat unit which is bonded to one or more repeat units B or B* or C via an inorganic siloxane bond, wherein B* is an organosiloxane repeat unit that does not have reactive organic components and may further have a protected functional group that may be deprotected after polymerization;
C is an inorganic repeat unit which is bonded to one or more repeat units B or B* or C via an inorganic bond; and
x and y and y* are positive numbers and z is a non negative number, wherein
when z=0, then 0.002≤x/(y+y*)≤210, and when z≠0, then 0.0003≤(y+y*)/z≤500 and 0.002≤x/(y+y*+z)≤210;
and wherein the inorganic/organic hybrid core 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, wherein each R 2 is attached to two or more silicon atoms;
p and q are each independently 0.0 to 2.0;
t is 0.5, 1.0, or 1.5;
d is 0 to about 30;
m is an integer from 2-20;
t
=
(
3
-
(
p
+
q
)
)
2
and p+q≤2
wherein the inorganic/organic hybrid surrounding material and the inorganic/organic hybrid core are composed of different materials.
2. 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 the surface a surface of the inorganic/organic hybrid 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 the surface of the inorganic/organic hybrid core.
3. The inorganic/organic hybrid material of claim 1 , wherein a pore structure of the inorganic/organic surrounding material comprises an ordered pore structure.
4. The inorganic/organic hybrid material of claim 1 , wherein the inorganic/organic surrounding material has a chromatographically enhancing pore geometry (CEPG).
5. The inorganic/organic hybrid material of claim 1 , wherein the inorganic/organic hybrid core is formed by hydrolytic condensation of one or more monomers selected from the group consisting of:
wherein
X is C 1 -C 18 alkoxy or C 1 -C 18 alkyl; and
n is 1-8.
6. A separations device having a stationary phase comprising the inorganic/organic hybrid material of claim 1 .
7. The separations device of claim 6 , wherein said device is selected from the group consisting of chromatographic columns, thin layer plates, filtration membranes, sample cleanup devices, solid supports, microchip separation devices, and microtiter plates.
8. The separations device of claim 7 , wherein the separations device is useful for applications selected from the group consisting of solid phase extraction, high pressure liquid chromatography, ultra high liquid chromatography, combinatorial chemistry, synthesis, biological assays, mass spectrometry, normal-phase separations, reversed-phase separations, HILIC separations, SFC separations, affinity separations, and SEC separations.
9. A chromatographic column, comprising
a) a column having a cylindrical interior for accepting a packing material and
b) a packed chromatographic bed comprising the inorganic/organic hybrid material of claim 1 .
10. The inorganic/organic hybrid surrounding material of claim 1 , wherein in formula I, R 1 is C 1 -C 18 alkyl group substituted by hydroxyl.
11. The inorganic/organic hybrid surrounding material of claim 10 , wherein R 1 is hydroxypropyl.
12. The inorganic/organic hybrid surrounding material of claim 10 , wherein a hydroxy substituted alkyl group is further functionalized by an isocyanate.
13. The inorganic/organic hybrid surrounding material of claim 12 , wherein the isocyanate is octadecyl isocyanate, dodecyl isocyanate, pentafluorophenyl isocyanate, 4-cyanophenyl isocyanate, 3-cyanophenyl isocyanate, 2-cyanophenyl isocyanate, phenyl isocyate, benzyl isocyanate, phenethyl isocyanate or diphenylethyl isocyante.