WO2010141426A1

WO2010141426A1 - Hybrid material for chromatographic separations

Info

Publication number: WO2010141426A1
Application number: PCT/US2010/036835
Authority: WO
Inventors: Kevin D. Wyndham
Original assignee: Waters Technologies Corporation
Priority date: 2009-06-01
Filing date: 2010-06-01
Publication date: 2010-12-09
Also published as: JP2015163895A; EP2437882A4; JP2012529054A; JP6151021B2; US20120055860A1; JP6364375B2; EP3964287A1; EP2437882A1; US20220203329A1; US11291974B2

Abstract

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.

Description

HYBRID MATERIAL FOR CHROMATOGRAPHIC SEPARATIONS

RELATED APPLICATION This application claims priority to U.S. provisional patent application Ser. No.

61/183,075, filed June 1, 2009, the entire disclosure of which is incorporated herein by this reference.

BACKGROUND OF THE INVENTION Packing materials for liquid chromatography (LC) are generally classified into two types: organic materials, e.g., polydivinylbenzene, and inorganic materials typified by silica. Many organic materials are chemically stable against strongly alkaline and strongly acidic mobile phases, allowing flexibility in the choice of mobile phase pH. However, organic chromatographic materials generally result in columns with low efficiency, particularly with low molecular-weight analytes. Many organic chromatographic materials not only lack the mechanical strength of typical chromatographic silicas and also shrink and swell when the composition of the mobile phase is changed.

Silica is the material most widely used in High Performance Liquid Chromatography (HPLC). The most common applications employ silica that has been surface-derivatized with an organic functional group such as octadecyl (C 18), octyl (C8), phenyl, amino, cyano, etc. As stationary phases for HPLC, these packing materials result in columns that have high efficiency and do not show evidence of shrinking or swelling.

There remains a need for alternative materials that provide additional mechanical strength, increased column efficiency, and chromatographic selectivity.

SUMMARY OF THE INVENTION

The present invention provides novel chromatographic materials, e.g. , for chromatographic separations, processes for its preparation and separations devices containing the chromatographic material. 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. In addition, by selecting a polyorganosiloxane (POS) with functional groups (e.g., pendant alkyl amines, alcohols, carboxylic acids, alkene or cyano group) that are relevant for a given chromatographic application, new hybrid materials may be prepared that have synthetically useful pendant groups near the surface of the particles.

Thus in one aspect, the invention provides an inorganic/organic hybrid material comprising an inorganic/organic hybrid surrounding material and an inorganic/organic hybrid core.

In certain aspects, the inorganic/organic hybrid surrounding material and the inorganic/organic hybrid core are composed of different materials. In other aspects the inorganic/organic hybrid surrounding material and the inorganic/organic hybrid core are composed of the same materials.

In yet other aspects the inorganic/organic hybrid surrounding material is composed of a material which enhances one or more of the characteristics selected from the group consisting of chromatographic selectivity, column chemical stability, column efficiency, and mechanical strength.. Similarly, in other aspects, the inorganic/organic hybrid core is composed of a material which enhances one or more characteristics selected from the group consisting of chromatographic selectivity, column chemical stability, column efficiency, and mechanical strength.

In other aspects, the inorganic/organic surrounding material is composed of a material which provides a change in hydrophilic/lipophilic balance (HLB), surface charge (e.g., isoelectric point or silanol pKa), and/or surface functionality for enhanced chromatographic separation. In still other aspects, the inorganic/organic hybrid surrounding material is independently derived from condensation of one or more polymeric organofunctional metal precursors, and/or polymeric metal oxide precursors on the surface of the hybrid 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 precursor(s) on the surface of the hybrid core .

In certain aspects, the inorganic portion of the inorganic/organic hybrid surrounding material is independently selected from the group consisting of alumina, silica, titania, cerium oxide, or zirconium oxides, and ceramic materials.

In still other aspects, the inorganic/organic hybrid surrounding material is independently derived from condensation of one or more organofunctional silanes and/or tetraalkoxysilane on the surface of the 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 (i.e., tetraethoxysilane, tetramethoxysilane) on the surface of the hybrid core. In some aspects, the inorganic/organic hybrid surrounding material may be independently porous or nonporous. Furthermore, the pore structure of the inorganic/organic hybrid surrounding material may independently possess or not possess an ordered pore structure. In certain aspects, the inorganic/organic hybrid surrounding material may have a chromatographically enhancing pore geometry (CEPG).

In other aspects, the inorganic/organic hybrid surrounding material may independently comprise from 0-100 mol% hybrid material. In specific aspects, the inorganic portion of the inorganic/organic hybrid surrounding material may independently be present in an amount ranging from about 0 molar % to not more than about 25 molar %, wherein the pores of the inorganic/organic hybrid surrounding material are substantially disordered. Similarly, the inorganic portion of the inorganic/organic hybrid surrounding material may independently be present in an amount ranging from about 25 molar % to not more than about 50 molar %, wherein the pores of the inorganic/organic hybrid surrounding material are substantially disordered, and wherein the inorganic/organic hybrid surrounding material independently possesses a chromatographically enhancing pore geometry (CEPG).

In some aspects, the inorganic/organic hybrid surrounding material may comprise a material of formula I:

(SiO₂)_d/[R²((R)_p(R¹)_qSiO_t)_m] ; (I) wherein, R and R¹ are each independently CpCi₈ alkoxy, CpCi₈ alkyl, CpCi₈ alkyl, C₂-Qg alkenyl, C₂-Ci₈ alkynyl, C₃-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, C₅-Ci₈ aryloxy, or CpCi₈ heteroaryl;

R² is Ci-Ci₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, C₃-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, CpCi₈ heteroaryl; or absent; wherein each R 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, R¹ and R² are optionally substituted; provided that:

(1) when R² is absent, m=l and t = (4-(p+q)), when 0<p+q < 3; and

2

(2) when R² is present, m=2-20 and t = (3-(p+q)), when p+q < 2 .

2 In other aspects, the inorganic/organic hybrid surrounding material may comprise a material of formula II : (SiO₂)_d/[(R)_p(R¹)_qSiO_t] (II); wherein,

R and R¹ are each independently Ci-Ci₈ alkoxy, CpCi₈ alkyl, CpCi₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, Cs-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, C₅-Ci₈ aryloxy, or CpCi₈ heteroaryl; d is 0 to about 30; p and q are each independently 0.0 to 3.0, provided that when p+q=l then t=l .5; when p+q=2 then t=l ; or when p+q=3 then t=0.5.

In still other aspects, the inorganic/organic hybrid surrounding material may comprise a material of formula III:

(SiOMR^R^SiOOJ (III) wherein,

R¹ is CpCi₈ alkoxy, CpCi₈ alkyl, CpCi₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, C₃-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, C₅-Ci₈ aryloxy, or CpCi₈ heteroaryl; R² is CpCi₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, C₃-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, CpCi₈ heteroaryl; or absent; wherein each R 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=l .5; or when r=l then t=l ; or when r=2 then t=0.5; and m is an integer from 1-20.

In yet aspects, the inorganic/organic hybrid surrounding material may comprise a material of 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 x +y + z = 1. In certain embodiments, 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.

In still yet other aspects, the inorganic/organic hybrid surrounding material may comprise a material of 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;

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 (i.e., polymerizable) 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 are positive numbers and z is a non negative number, wherein x +y + z = 1. In certain embodiments, 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.

In some aspects, the hybrid content of the hybrid core ranges from 1-100 mol% hybrid or from 4-100 mol% hybrid. In certain aspects, the structure of the hybrid core may independently possess or not possess a copolymeric structure. Similarly, the pore structure of the hybrid core may independently to possess or not possess an ordered pore structure. In certain aspects, the hybrid core may be porous or non-porous.

In some aspects, the hybrid core has formula I:

(SiO₂)_d/[R²((R)_p(R¹)_qSiO_t)_m] ; (I) wherein,

R and R¹ are each independently CpCi₈ alkoxy, CpCi₈ alkyl, CpCi₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, Cs-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, C₅-Ci₈ aryloxy, or CpCi₈ heteroaryl; R² is Ci-Ci₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, C₃-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, CpCi₈ heteroaryl; or absent; wherein each R 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, R¹ and R² are optionally substituted; provided that:

(1) when R² is absent, m=l and t = (4-(p+q)), when 0<p+q < 3; and 2

(2) when R² is present, m=2-20 and t = (3-(p+q)), when p+q < 2 .

2 In other aspects, the hybrid core has formula II :

(SiOMCR^R^SiOt] (II); wherein,

R and R¹ are each independently CpCi₈ alkoxy, CpCi₈ alkyl, CpCi₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, C₃-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, C₅-Ci₈ aryloxy, or CpCi₈ heteroaryl; d is 0 to about 30; p and q are each independently 0.0 to 3.0, provided that when p+q=l then t=1.5; when p+q=2 then t=l ; or when p+q=3 then t=0.5.

In still other aspects, the hybrid core has formula III:

(SiOMR^R^SiOOJ (III) wherein, R¹ is CpCi₈ alkoxy, CpCi₈ alkyl, CpCi₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, C₃-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, C₅-Ci₈ aryloxy, or CpCi₈ heteroaryl;

R² is CpCi₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, C₃-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, CpCi₈ heteroaryl; or absent; wherein each R 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=l .5; or when r=l then t=l ; or when r=2 then t=0.5; and m is an integer from 1-20.

In still yet other aspects, the hybrid core has 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;

In yet other aspects, the hybrid core has formula V:

In certain aspects, the invention provides an inorganic/organic hybrid material wherein the hybrid core and/or the inorganic/organic hybrid surrounding material is a porous hybrid inorganic/organic material comprising ordered domains have formula IV, V or VI below:

(A)χ(B)_y(C)_z (Formula IV) wherein the order of repeat units A, B, and C may be random, block, or a combination of random and block;

C is an inorganic repeat unit which is bonded to one or more repeat units B or C via an inorganic bond; and x, y are positive numbers and z is a non negative number, wherein x +y + z = 1. In certain embodiments, 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;

(A)χ(B)_y(B*)_y*(C)_z (Formula V) wherein the order of repeat units A, B, B*, and C may be random, block, or a combination of random and block;

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 (i.e., polymerizable) 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, y are positive numbers and z is a non negative number, wherein x +y + z = 1. In certain embodiments, 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; or

[A]_y[B]_x (Formula VI), wherein x and y are whole number integers and A is SiO₂/(R¹ _pR² _qSiO_t)_n or SiO₂/[R³(R¹ _rSiO_t)_m]_n; wherein R¹ and R² are independently a substituted or unsubstituted Ci to C₇ alkyl group, or a substituted or unsubstituted aryl group, R³ is a substituted or unsubstituted Ci to C₇ alkyl, alkenyl, alkynyl, or arylene group bridging two or more silicon atoms, p and q are 0, 1 , or 2, provided that p + q = 1 or 2, and that when p + q = 1, t = 1.5, and when p + q = 2, t = 1 ; r is O or 1 , provided that when r = 0, t = 1.5, and when r = 1 , t = 1 ; m is an integer greater than or equal to 2; and n is a number from 0.01 to 100; B is :

SiO₂/(R⁴vSiO_t)_n wherein R⁴ is hydroxyl, fluorine, alkoxy, aryloxy, substituted siloxane, protein, peptide, carbohydrate, nucleic acid, or combinations thereof, R⁴ is not R¹, R², or R³; v is 1 or 2, provided that when v = 1, t = 1.5, and when v=2, t =1; and n is a number from 0.01 to 100; wherein the material of formula VI has an interior area and an exterior surface, and said interior area of said material has a composition represented by A; said exterior surface of said material has a composition represented by A and B, and wherein said exterior composition is between about 1 and about 99% of the composition of B and the remainder comprising A.

In some aspects, the invention provides an inorganic/organic hybrid material in which the hybrid core is a monolith, a particle, a spherical particle, or a pellicular particle.

In other aspects, the invention provides an inorganic/organic hybrid material which has been surface modified by coating with a polymer. In certain aspects, the inorganic/organic hybrid material has been surface modified with a surface modifier having the formula Z_a(R')bSi-R", where Z = Cl, Br, I, Cl - C5 alkoxy, dialkylamino or trifluoromethanesulfonate; a and b are each an integer from 0 to 3 provided that a + b = 3; R' is a Ci - Cβ straight, cyclic or branched alkyl group, and R" is a functionalizing group.

In certain aspects, the invention provides an inorganic/organic hybrid material further comprising a nanoparticle dispersed within the hybrid core and/or the inorganic/organic hybrid surrounding material. In other aspects, the nanoparticle may be a mixture of more than one nanoparticle and may be crystalline or amorphous. In still other aspects, the nanoparticle may be silicon carbide, aluminum, diamond, cerium, carbon black, carbon nanotubes, zirconium, barium, cerium, cobalt, copper, europium, gadolinium, iron, nickel, samarium, silicon, silver, titanium, zinc, boron, oxides thereof, and nitrides thereof.

In another aspect, the invention provides, an inorganic/organic hybrid particle comprising a hybrid particle core with an inorganic/organic hybrid surrounding material wherein said particle has the formula

(Y(CHz)_nSiOi S)_x(O₁5SiCH₂CH₂SiO_{1 5})_y(Si0₂)_z wherein: each Y is independently -OH, -NH₂, -NR₂, -NR₂R⁵⁺, SH, S(OV₂R, S(OV₂O^", C₁-C₁₈ alkoxy, C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₁-C₁₈ heterocycloalkyl, C₅-Ci₈ aryl, C₅-Ci₈ aryloxy, or CpCi₈ heteroarylaryl, CpCi₈ alkoxy, CpCi₈ alkyl, CpCi₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, Cs-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, C₅-Ci₈ aryloxy, or CpCi₈ heteroaryl; each R and R are independently CpCi₈ alkoxy, CpCi₈ alkyl, CpCi₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, C₃-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, C₅-Ci₈ aryloxy, or CpCi₈ heteroaryl; n is from 0 to 18; x, y and z are independently from about 0.0 to about 1.0 wherein y+z is 1.0-x and y is from about 3.0 to about 5.0 times greater than z. In certain aspects, Y is -OH and n is 3. In other aspects, x is 1.0. In still other aspects Y is -OH, n is 3 and x is 1.0. In still other aspects n is from 3 to 12, or from 3 to 8

In another aspect, the invention provides a method for preparing an inorganic/organic hybrid material comprising an inorganic/organic hybrid core and an inorganic/organic hybrid surrounding material comprising the steps of: providing a hybrid core material; and condensing one or more polymeric organofunctional metal precursors, and/or polymeric metal oxide precursors on the surface of the hybrid core

In still another aspect, the invention provides a method for preparing an inorganic/organic hybrid material comprising an inorganic/organic hybrid core and an inorganic/organic hybrid surrounding material comprising the steps of: providing a hybrid core material; applying a 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 on the surface of the hybrid core; and further condensing said surface.

In another aspect, the invention provides a method for preparing an inorganic/organic hybrid material comprising an inorganic/organic hybrid core and an inorganic/organic hybrid surrounding material comprising the steps of: providing a hybrid core material; and condensing one or more polymeric organofunctional metal precursors, and/or polymeric metal oxide precursors on the surface of the hybrid core. In yet another aspect, the invention provides a method for preparing an inorganic/organic hybrid material comprising an inorganic/organic hybrid core and an inorganic/organic hybrid surrounding material comprising the steps of: providing a hybrid core material; applying a 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 on the surface of the hybrid core; and further condensing said surface. In certain aspects, the hybrid core material utilized in the methods of producing a hybrid material may be provided by the steps of: a) hydrolytically condensing one or more monomers selected from the group consisting of organoalkoxysilanes and tetraalkoxysilanes, with one or more monomers selected from the group consisting of organoalkoxysilanes, tetraalkoxysilanes, metal oxide precursors and ceramic precursors, to produce a polyorganoalkoxysiloxane; b) further condensing the polyorganoalkoxysiloxane to form a spherical porous particle; and c) subjecting the resulting particle to hydrothermal treatment; to thereby produce a porous inorganic/organic hybrid core material. In other aspects, the hybrid core material utilized in the methods of producing a hybrid material may be provided by the steps of:

(a) hydrolytically condensing an alkenyl-functionalized organosilane with a tetraalkoxysilane;

(b) copolymerizing the product of step (a) with an organic olefin monomer; and (c) further condensing the product of step (b) to form a spherical porous particle.

In still other aspects, the hybrid core material utilized in the methods of producing a hybrid material may be provided by the steps of:

(a) copolymerizing an organic olefin monomer with an alkenyl-functionalized organosilane; and (b) hydrolytically condensing the product of step (a) with a tetraalkoxysilane in the presence of a non-optically active porogen; and

(c) further condensing the product of step (b) to form a spherical porous particle. In other aspects, the invention provides a separations device having a stationary phase comprising the inorganic/organic hybrid material of the invention. In certain aspects, the separations device may be a chromatographic column, a thin layer plate, a filtration membrane, a sample cleanup device, a solid support, a microchip separation device, or a microtiter plate. In still other aspects, the separations device may be useful for solid phase extraction, high pressure liquid chromatography, ultra high liquid chromatography, combinatorial chemistry, synthesis, biological assays, or mass spectrometry. In another aspect, the invention provides 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 the invention.

BRIEF DESCRIPTION OF THE FIGURES

Figure 1 is a desorption pore diameter comparison of products 8b, 9b and the unmodified hybrid core from multi-point N₂ sorption analysis.

DETAILED DESCRIPTION OF THE INVENTION The present invention provides novel chromatographic materials, e.g. , for chromatographic separations, processes for its preparation and separations devices containing the chromatographic material. The preparation of the materials of the invention wherein the 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. In addition, by selecting a polyorganosiloxane (POS) with functional groups (e.g., pendant alkyl amines, alcohols, carboxylic acids, alkene or cyano group) that are relevant for a given chromatographic application, new hybrid materials may be prepared that have synthetically useful pendant groups near the surface of the particles.

The present invention will be more fully illustrated by reference to the definitions set forth below.

Definitions "Hybrid" includes inorganic-based structures wherein an organic functionality is integral to both the internal or "skeletal" inorganic structure as well as the hybrid material surface. The inorganic portion of the hybrid material may be, e.g., alumina, silica, titanium, cerium, or "Hybrid" includes inorganic-based structures wherein an organic functionality is integral to both the internal or "skeletal" inorganic structure as well as the hybrid material surface. The inorganic portion of the hybrid material may be, e.g., alumina, silica, titanium, cerium, or zirconium oxides, or ceramic material; in a preferred embodiment, the inorganic portion of the hybrid material is silica. As noted above, exemplary hybrid materials are shown in U.S. Patent Nos. 4,017,528, 6,528,167, 6,686,035 and 7,175,913.

"Hybrid core" includes a hybrid material, as defined herein, in the form of a particle, a monolith or another suitable structure which forms the internal portion of the inorganic/organic hybrid materials comprising an inorganic/organic hybrid surrounding material of the invention. "Inorganic/organic hybrid surrounding material" includes a hybrid material, as defined herein, which surrounds the hybrid core. The inorganic/organic hybrid surrounding material may surround the hybrid core entirely, thus encapsulating the hybrid core or may only partially surround the hybrid core, thus leaving a surface of the hybrid core exposed at one or more positions on the surface area of the hybrid core. The inorganic/organic hybrid surrounding material may be disposed on or bonded to or annealed to the hybrid core in such a way that a discrete or distinct transition is discernable or may be bound to the hybrid core in such a way as to blend with the surface of the hybrid core resulting in a gradation of materials, and no discrete internal core surface. In certain embodiments, the inorganic/organic hybrid surrounding material may be the same or different from the material of the hybrid core. In certain embodiments , including those in which the inorganic/organic hybrid surrounding material and the inorganic/organic hybrid core are composed of the same materials, the surrounding material may exhibit different physical or physiochemical properties, including, but not limited to, micropore volume, micropore surface area, average pore diameter, carbon content or hydrolytic pH stability. The term "alicyclic group" includes closed ring structures of three or more carbon atoms. Alicyclic groups include cycloparaffms or naphthenes which are saturated cyclic hydrocarbons, cycloolefins, which are unsaturated with two or more double bonds, and cycloacetylenes which have a triple bond. They do not include aromatic groups. Examples of cycloparaffms include cyclopropane, cyclohexane and cyclopentane. Examples of cycloolefins include cyclopentadiene and cyclooctatetraene. Alicyclic groups also include fused ring structures and substituted alicyclic groups such as alkyl substituted alicyclic groups. In the instance of the alicyclics such substituents can further comprise a lower alkyl, a lower alkenyl, a lower alkoxy, a lower alkylthio, a lower alkylamino, a lower alkylcarboxyl, a nitro, a hydroxyl, -CF3, -CN, or the like. The term "aliphatic group" includes organic compounds characterized by straight or branched chains, typically having between 1 and 22 carbon atoms. Aliphatic groups include alkyl groups, alkenyl groups and alkynyl groups. In complex structures, the chains can be branched or cross-linked. Alkyl groups include saturated hydrocarbons having one or more carbon atoms, including straight-chain alkyl groups and branched-chain alkyl groups. Such hydrocarbon moieties may be substituted on one or more carbons with, for example, a halogen, a hydroxyl, a thiol, an amino, an alkoxy, an alkylcarboxy, an alkylthio, or a nitro group. Unless the number of carbons is otherwise specified, "lower aliphatic" as used herein means an aliphatic group, as defined above (e.g., lower alkyl, lower alkenyl, lower alkynyl), but having from one to six carbon atoms. Representative of such lower aliphatic groups, e.g., lower alkyl groups, are methyl, ethyl, n-propyl, isopropyl, 2-chloropropyl, n-butyl, sec-butyl, 2-aminobutyl, isobutyl, tert-butyl, 3- thiopentyl and the like. As used herein, the term "nitro" means -NO2; the term "halogen" designates -F, -Cl, -Br or -I; the term "thiol" means SH; and the term "hydroxyl" means -OH. Thus, the term "alkylamino" as used herein means an alkyl group, as defined above, having an amino group attached thereto. Suitable alkylamino groups include groups having 1 to about 12 carbon atoms, preferably from 1 to about 6 carbon atoms. The term "alkylthio" refers to an alkyl group, as defined above, having a sulfhydryl group attached thereto. Suitable alkylthio groups include groups having 1 to about 12 carbon atoms, preferably from 1 to about 6 carbon atoms. The term "alkylcarboxyl" as used herein means an alkyl group, as defined above, having a carboxyl group attached thereto. The term "alkoxy" as used herein means an alkyl group, as defined above, having an oxygen atom attached thereto. Representative alkoxy groups include groups having 1 to about 12 carbon atoms, preferably 1 to about 6 carbon atoms, e.g., methoxy, ethoxy, propoxy, tert-butoxy and the like. The terms "alkenyl" and "alkynyl" refer to unsaturated aliphatic groups analogous to alkyls, but which contain at least one double or triple bond respectively. Suitable alkenyl and alkynyl groups include groups having 2 to about 12 carbon atoms, preferably from 1 to about 6 carbon atoms.

The term "alkyl" includes saturated aliphatic groups, including straight-chain alkyl groups, branched-chain alkyl groups, cycloalkyl (alicyclic) groups, alkyl substituted cycloalkyl groups and cycloalkyl substituted alkyl groups. In certain embodiments, a straight chain or branched chain alkyl has 30 or fewer carbon atoms in its backbone, e.g., C1-C30 for straight chain or C3-C30 for branched chain. In certain embodiments, a straight chain or branched chain alkyl has 20 or fewer carbon atoms in its backbone , e.g., C1-C20 for straight chain or C3-C20 for branched chain, and more preferably 18 or fewer. Likewise, preferred cycloalkyls have from 4-10 carbon atoms in their ring structure and more preferably have 4-7 carbon atoms in the ring structure. The term "lower alkyl" refers to alkyl groups having from 1 to 6 carbons in the chain and to cycloalkyls having from 3 to 6 carbons in the ring structure.

Moreover, the term "alkyl" (including "lower alkyl") as used throughout the specification and claims includes both "unsubstituted alkyls" and "substituted alkyls", the latter of which refers to alkyl moieties having substituents replacing a hydrogen on one or more carbons of the hydrocarbon backbone. Such substituents can include, for example, halogen, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate, phosphonato, phosphinato, cyano, amino (including alkyl amino, dialkylamino, arylamino, diarylamino and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido), amidino, imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfate, sulfonato, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclyl, aralkyl, or an aromatic or heteroaromatic moiety. It will be understood by those skilled in the art that the moieties substituted on the hydrocarbon chain can themselves be substituted, if appropriate. Cycloalkyls can be further substituted, e.g., with the substituents described above. An "aralkyl" moiety is an alkyl substituted with an aryl, e.g., having 1 to 3 separate or fused rings and from 6 to about 18 carbon ring atoms, e.g., phenylmethyl (benzyl).

The term "amino," as used herein, refers to an unsubstituted or substituted moiety of the formula -NRaRb, in which Ra and Rb are each independently hydrogen, alkyl, aryl, or heterocyclyl, or Ra and Rb, taken together with the nitrogen atom to which they are attached, form a cyclic moiety having from 3 to 8 atoms in the ring. Thus, the term "amino" includes cyclic amino moieties such as piperidinyl or pyrrolidinyl groups, unless otherwise stated. An "amino- substituted amino group" refers to an amino group in which at least one of Ra and Rb, is further substituted with an amino group.

The term "aromatic group" includes unsaturated cyclic hydrocarbons containing one or more rings. Aromatic groups include 5- and 6-membered single-ring groups which may include from zero to four heteroatoms, for example, benzene, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, triazole, pyrazole, pyridine, pyrazine, pyridazine and pyrimidine and the like. The aromatic ring may be substituted at one or more ring positions with, for example, a halogen, a lower alkyl, a lower alkenyl, a lower alkoxy, a lower alkylthio, a lower alkylamino, a lower alkylcarboxyl, a nitro, a hydroxyl, -CF3, -CN, or the like. The term "aryl" includes 5- and 6-membered single-ring aromatic groups that may include from zero to four heteroatoms, for example, unsubstituted or substituted benzene, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, triazole, pyrazole, pyridine, pyrazine, pyridazine and pyrimidine and the like. Aryl groups also include polycyclic fused aromatic groups such as naphthyl, quinolyl, indolyl and the like. The aromatic ring can be substituted at one or more ring positions with such substituents, e.g., as described above for alkyl groups. Suitable aryl groups include unsubstituted and substituted phenyl groups. The term "aryloxy" as used herein means an aryl group, as defined above, having an oxygen atom attached thereto. The term "aralkoxy" as used herein means an aralkyl group, as defined above, having an oxygen atom attached thereto. Suitable aralkoxy groups have 1 to 3 separate or fused rings and from 6 to about 18 carbon ring atoms, e.g., O-benzyl. The terms "as made" and "freshmade" are used interchangeably and refer to particles obtained after the gelation process but prior to hydrothermal treatment.

The term "ceramic precursor" " is intended include any compound that results in the formation of a ceramic material. The term "chiral moiety" is intended to include any functionality that allows for chiral or stereoselective syntheses. Chiral moieties include, but are not limited to, substituent groups having at least one chiral center, natural and unnatural amino-acids, peptides and proteins, derivatized cellulose, macrocyclic antibiotics, cyclodextrins, crown ethers, and metal complexes. The language "chromatographically-enhancing pore geometry" includes the geometry of the pore configuration of the presently-disclosed materials, which has been found to enhance the chromatographic separation ability of the material, e.g., as distinguished from other chromatographic media in the art. For example, a geometry can be formed, selected or constructed, and various properties and/or factors can be used to determine whether the chromatographic separations ability of the material has been "enhanced", e.g., as compared to a geometry known or conventionally used in the art. Examples of these factors include high separation efficiency, longer column life and high mass transfer properties (as evidenced by, e.g., reduced band spreading and good peak shape.) These properties can be measured or observed using art-recognized techniques. For example, the chromatographically-enhancing pore geometry of the present porous inorganic/organic hybrid particles is distinguished from the prior art particles by the absence of "ink bottle" or "shell shaped" pore geometry or morphology, both of which are undesirable because they, e.g., reduce mass transfer rates, leading to lower efficiencies.

Chromatographically-enhancing pore geometry is found in hybrid materials containing only a small population of micropores. A small population of micropores is achieved in hybrid materials when all pores of a diameter of about < 34A contribute less than about 110 m^/g to the specific surface area of the material. Hybrid materials with such a low micropore surface area (MSA) give chromatographic enhancements including high separation efficiency and good mass transfer properties (as evidenced by, e.g., reduced band spreading and good peak shape). Micropore surface area (MSA) is defined as the surface area in pores with diameters less than or equal to 34A, determined by multipoint nitrogen sorption analysis from the adsorption leg of the isotherm using the BJH method. As used herein, the acronyms "MSA" and "MPA" are used interchangeably to denote "micropore surface area".

The term "functionalizing group" includes organic functional groups which impart a certain chromatographic functionality to a chromatographic stationary phase.

The term "heterocyclic group" includes closed ring structures in which one or more of the atoms in the ring is an element other than carbon, for example, nitrogen, sulfur, or oxygen. Heterocyclic groups can be saturated or unsaturated and heterocyclic groups such as pyrrole and furan can have aromatic character. They include fused ring structures such as quinoline and isoquinoline. Other examples of heterocyclic groups include pyridine and purine. Heterocyclic groups can also be substituted at one or more constituent atoms with, for example, a halogen, a lower alkyl, a lower alkenyl, a lower alkoxy, a lower alkylthio, a lower alkylamino, a lower alkylcarboxyl, a nitro, a hydroxyl, -CF3, -CN, or the like. Suitable heteroaromatic and heteroalicyclic groups generally will have 1 to 3 separate or fused rings with 3 to about 8 members per ring and one or more N, O or S atoms, e.g. coumarinyl, quinolinyl, pyridyl, pyrazinyl, pyrimidyl, furyl, pyrrolyl, thienyl, thiazolyl, oxazolyl, imidazolyl, indolyl, benzofuranyl, benzothiazolyl, tetrahydrofuranyl, tetrahydropyranyl, piperidinyl, morpholino and pyrrolidinyl.

The term "metal oxide precursor" is intended include any compound that contains a metal and results in the formation of a metal oxide, e.g., alumina, silica, titanium oxide, zirconium oxide. The term "monolith" is intended to include a collection of individual particles packed into a bed formation, in which the shape and morphology of the individual particles are maintained. The particles are advantageously packed using a material that binds the particles together. Any number of binding materials that are well known in the art can be used such as, for example, linear or cross-linked polymers of divinylbenzene, methacrylate, urethanes, alkenes, alkynes, amines, amides, isocyanates, or epoxy groups, as well as condensation reactions of organoalkoxysilanes, tetraalkoxysilanes, polyorganoalkoxysiloxanes, polyethoxysiloxanes, and ceramic precursors. In certain embodiments, the term "monolith" also includes hybrid monoliths made by other methods, such as hybrid monoliths detailed in US Patent No. 7,250,214; hybrid monoliths prepared from the condensation of one or more monomers that contain 0-99 mole percent silica (e.g., SiO2); hybrid monoliths prepared from coalesced porous inorganic/organic particles; hybrid monoliths that have a chromatographically-enhancing pore geometry; hybrid monoliths that do not have a chromatographically-enhancing pore geometry; hybrid monoliths that have ordered pore structure; hybrid monoliths that have non-periodic pore structure; hybrid monoliths that have non-crystalline or amorphous molecular ordering; hybrid monoliths that have crystalline domains or regions; hybrid monoliths with a variety of different macropore and mesopore properties; and hybrid monoliths in a variety of different aspect ratios. In certain embodiments, the term "monolith" also includes inorganic monoliths, such as those described in G. Guiochon /J. Chromatogr. A 1168 (2007) 101-168.

The term "nanoparticle" is a microscopic particle/grain or microscopic member of a powder/nanopowder with at least one dimension less than about 100 nm, e.g., a diameter or particle thickness of less than about 100 nm (0.1 mm), which may be crystalline or noncrystalline. Nanoparticles have properties different from, and often superior to those of conventional bulk materials including, for example, greater strength, hardness, ductility, sinterability, and greater reactivity among others. Considerable scientific study continues to be devoted to determining the properties of nanomaterials, small amounts of which have been synthesized (mainly as nano-size powders) by a number of processes including colloidal precipitation, mechanical grinding, and gas-phase nucleation and growth. Extensive reviews have documented recent developments in nano-phase materials, and are incorporated herein by reference thereto: Gleiter, H. (1989) "Nano- crystalline materials," Prog. Mater. Sci. 33:223-315 and Siegel, R. W. (1993) "Synthesis and properties of nano-phase materials," Mater. Sci. Eng. A168:189-197. In certain embodiments, the nanoparticles comprise oxides or nitrides of the following: silicon carbide, aluminum, diamond, cerium, carbon black, carbon nanotubes, zirconium, barium, cerium, cobalt, copper, europium, gadolinium, iron, nickel, samarium, silicon, silver, titanium, zinc, boron, and mixtures thereof. In certain embodiments, the nanoparticles of the present invention are selected from diamonds, zirconium oxide (amorphous, monoclinic, tetragonal and cubic forms), titanium oxide

(amorphous, anatase, brookite and rutile forms), aluminum (amorphous, alpha, and gamma forms), and boronitride (cubic form). In particular embodiments, the nanoparticles of the present invention are selected from nano-diamonds, silicon carbide, titanium dioxide (anatase form), cubic-boronitride, and any combination thereof. Moreover, in particular embodiments, the nanoparticles may be crystalline or amorphous. In particular embodiments, the nanoparticles are less than or equal to 100 mm in diameter, e.g., less than or equal to 50 mm in diameter, e.g., less than or equal to 20 mm in diameter.

Moreover, it should be understood that the nanoparticles that are characterized as dispersed within the composites of the invention are intended to describe exogenously added nanoparticles. This is in contrast to nanoparticles, or formations containing significant similarity with putative nanoparticles, that are capable of formation in situ, wherein, for example, macromolecular structures, such as particles, may comprise an aggregation of these endogenously created.

The term "substantially disordered" refers to a lack of pore ordering based on x-ray powder diffraction analysis. Specifically, "substantially disordered" is defined by the lack of a peak at a diffraction angle that corresponds to a d value (or d-spacing) of at least 1 nm in an x-ray diffraction pattern.

"Surface modifiers" include (typically) organic functional groups which impart a certain chromatographic functionality to a chromatographic stationary phase. The porous inorganic/organic hybrid particles possess both organic groups and silanol groups which may additionally be substituted or derivatized with a surface modifier.

The language "surface modified" is used herein to describe the composite material of the present invention that possess both organic groups and silanol groups which may additionally be substituted or derivatized with a surface modifier. "Surface modifiers" include (typically) organic functional groups which impart a certain chromatographic functionality to a chromatographic stationary phase. Surface modifiers such as disclosed herein are attached to the base material, e.g., via derivatization or coating and later crosslinking, imparting the chemical character of the surface modifier to the base material. In one embodiment, the organic groups of a hybrid material, e.g., particle, react to form an organic covalent bond with a surface modifier. The modifiers can form an organic covalent bond to the material's organic group via a number of mechanisms well known in organic and polymer chemistry including but not limited to nucleophilic, electrophilic, cycloaddition, free-radical, carbene, nitrene, and carbocation reactions. Organic covalent bonds are defined to involve the formation of a covalent bond between the common elements of organic chemistry including but not limited to hydrogen, boron, carbon, nitrogen, oxygen, silicon, phosphorus, sulfur, and the halogens. In addition, carbon-silicon and carbon-oxygen-silicon bonds are defined as organic covalent bonds, whereas silicon-oxygen- silicon bonds that are not defined as organic covalent bonds. A variety of synthetic transformations are well known in the literature, see, e.g., March, J. Advanced Organic Chemistry, 3rd Edition, Wiley, New York, 1985.

Inorganic/Organic Hybrid Materials

The invention provides an inorganic/organic hybrid material comprising a inorganic/organic hybrid core and an inorganic/organic surrounding material The composition of the surrounding material may be varied by one of ordinary skill in the art to provide enhanced chromatographic selectivity, enhanced column chemical stability, enhanced column efficiency, and/or enhanced mechanical strength. Similarly, the composition of the surrounding material provides a change in hydrophilic/lipophilic balance (HLB), surface charge (e.g., isoelectric point or silanol pKa), and/or surface functionality for enhanced chromatographic separation. Furthermore, in some embodiments, the composition of the surrounding material may also provide a surface functionality for available for further surface modification.

The surrounding material may be independently derived from condensation of one or more polymeric organo functional metal precursors, and/or polymeric metal oxide precursors on the surface of the hybrid 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 the surface of the hybrid core. In certain aspects, the inorganic portion of the surrounding material is independently selected from the group consisting of alumina, silica, titania, cerium oxide, or zirconium oxides, and ceramic materials.

Alternatively, the surrounding material may independently derived from condensation of one or more organofunctional silanes and/or tetraalkoxysilane on the surface of the 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 (i.e., tetraethoxysilane, tetramethoxysilane) on the surface of the hybrid core.

The surrounding material may be independently porous or nonporous. Furthermore, the pore structure of the surrounding material may independently possess or not possess an ordered pore structure. In certain aspects, the surrounding material may have a chromatographically enhancing pore geometry (CEPG).

In other aspects, the surrounding material may independently comprise from about 0-100 mol% hybrid material . The inorganic portion of the surrounding material may independently be alumina, silica, titanium oxide, cerium oxide, zirconium oxide or ceramic materials or a mixture thereof.

In specific aspects, the inorganic portion of the surrounding material may independently be present in an amount ranging from about 0 molar % to not more than about 25 molar %, wherein the pores of the surrounding material are substantially disordered. Similarly, the inorganic portion of the surrounding material may independently be present in an amount ranging from about 25 molar % to not more than about 50 molar %, wherein the pores of the surrounding material are substantially disordered, and wherein the surrounding material independently possesses a chromatographically enhancing pore geometry (CEPG). In certain embodiments, the inorganic portion of the surrounding material may independently be present in an amount ranging from about 50 molar % to not more than about 75 molar %, wherein the pores of the surrounding material are substantially disordered, and wherein the surrounding material independently possesses a chromatographically enhancing pore geometry (CEPG). In still other embodiments, the inorganic portion of the surrounding material may independently be present in an amount ranging from about 75 molar % to not more than about 100 molar %, wherein the pores of the surrounding material are substantially disordered, and wherein the surrounding material independently possesses a chromatographically enhancing pore geometry (CEPG).

In some aspects, the surrounding material may comprise a material of formula I:

(SiO₂)_d/[R²((R)_p(R¹)_qSiO_t)_m] ; (I) wherein,

R and R¹ are each independently CpCi₈ alkoxy, CpCi₈ alkyl, CpCi₈ alkyl, C₂-C₁8 alkenyl, C₂-Ci₈ alkynyl, C₃-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, C₅-Ci₈ aryloxy, or CpCi₈ heteroaryl;

(1) when R² is absent, m=l and t = (4-(p+q)), when 0<p+q < 3; and

2

(2) when R² is present, m=2-20 and t = (3-(p+q)), when p+q < 2 . 2

In other aspects, the surrounding material may comprise a material of formula II :

(SiOMCR^R^SiOt] (II); wherein,

R and R¹ are each independently CpCi₈ alkoxy, CpCi₈ alkyl, CpCi₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, C₃-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, C₅-Ci₈ aryloxy, or CpCi₈ heteroaryl; d is 0 to about 30; p and q are each independently 0.0 to 3.0, provided that when p+q=l then t=1.5; when p+q=2 then t=l ; or when p+q=3 then t=0.5. In still other aspects, the surrounding material may comprise a material of formula III:

(SiOMR^R^SiOOJ (III) wherein,

R¹ is CpCi₈ alkoxy, CpCi₈ alkyl, CpCi₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, C₃-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, C₅-Ci₈ aryloxy, or CpCi₈ heteroaryl; R² is Ci-Ci₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, C₃-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, CpCi₈ heteroaryl; or absent; wherein each R 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=l .5; or when r=l then t=l ; or when r=2 then t=0.5; and m is an integer from 1-20.

In yet aspects, the surrounding material may comprise a material of formula IV:

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 x + y + z = 1. In certain embodiments, 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.

In still yet other aspects, the surrounding material may comprise a material of formula V:

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 (i.e., polymerizable) 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 are positive numbers and z is a non negative number, wherein x + y + y* +z = 1. In certain embodiments, 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.

In certain aspects, R in the formulas presented above may be present or absent.

In certain aspects, R¹ in the formulas presented above is Ci-Ci₈ alkyl group substituted by hydroxyl. In still other aspects, R¹ in the formulas presented above is hydroxypropyl. In still other aspects, the hydroxy substituted alkyl group is further functionalized by an isocyanate. In yet other aspects, 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.

In another aspect, the invention provides materials as described herein wherein the surrounding material further comprises a nanoparticle or a mixture of more than one nanoparticles dispersed within the hybrid core.

In certain embodiments, the nanoparticle is present in <20% by weight of the nanocomposite, <10% by weight of the nanocomposite, or <5% by weight of the nanocomposite.

In other embodiments, the nanoparticle is crystalline or amorphous and may be silicon carbide, aluminum, diamond, cerium, carbon black, carbon nanotubes, zirconium, barium, cerium, cobalt, copper, europium, gadolinium, iron, nickel, samarium, silicon, silver, titanium, zinc, boron, oxides thereof, or a nitride thereof. In particular embodiments, the nanoparticle is a substance which comprises one or more moieties selected from the group consisting of nano- diamonds, silicon carbide, titanium dioxide, cubic-boronitride.

In other embodiments, the nanoparticles may be less than or equal to 200 μm in diameter, less than or equal to 100 μm in diameter, less than or equal to 50 μm in diameter, or less than or equal to 20 μm in diameter.

Hybrid Core

The novel inorganic/organic hybrid materials of the invention comprise an inorganic/organic hybrid surrounding material and a porous or non-porous inorganic/organic hybrid core. The hybrid core may possess or not possess a copolymeric structure and may or may not possess an ordered pore structure (if porous).

Thus, in one aspect, the invention comprises an inorganic/organic hybrid core, wherein the inorganic portion of the hybrid core is present in an amount ranging from about 0 molar % to not more than about 100 molar %, wherein the pores of the core are substantially disordered. In other embodiments, the inorganic portion of the hybrid core is present in an amount from about 0 molar % to not more than about 75 molar %. In still other embodiments, the inorganic portion of the hybrid core is present in an amount from about 0 molar % to not more than about 50 molar %. In yet other embodiments, the inorganic portion of the hybrid core is present in an amount from about 0 molar % to not more than about 25 molar %.

In various embodiments of the aforementioned aspect of the invention, the amount of the inorganic portion of the hybrid core ranges from: about 0 molar % to not more than about 1 molar %; about 0 molar % to not more than about 2 molar %; about 0 molar % to not more than about 3 molar %; about 0 molar % to not more than about 4 molar %; about 0 molar % to not more than about 5 molar %; about 0 molar % to not more than about 6 molar %; about 0 molar % to not more than about 7 molar %; about 0 molar % to not more than about 8 molar %; about 0 molar % to not more than about 9 molar %; about 0 molar % to not more than about 10 molar %; about 0 molar % to not more than about 11 molar %; about 0 molar % to not more than about 12 molar %; about 0 molar % to not more than about 13 molar %; about 0 molar % to not more than about 14 molar %; about 0 molar % to not more than about 15 molar %; about 0 molar % to not more than about 16 molar % ; about 0 molar % to not more than about 17 molar % ; about 0 molar % to not more than about 18 molar %; about 0 molar % to not more than about 19 molar %; about 0 molar % to not more than about 20 molar % ; about 0 molar % to not more than about 21 molar %; about 0 molar % to not more than about 22 molar % ; about 0 molar % to not more than about 23 molar % ; about 0 molar % to not more than about 24 molar %; and about 0 molar % to not more than about 25 molar.

In another aspect, the invention provides an inorganic/organic hybrid core, wherein the inorganic portion of the hybrid core is present in an amount ranging from about 0 molar % to not more than about 100 molar %, wherein the pores of the hybrid core are substantially disordered and wherein the hybrid core has a chromatographically enhancing pore geometry (CEPG). In another embodiment, the inorganic portion of the hybrid core is present in an amount ranging from about 25 molar % to not more than about 50 molar %, wherein the pores of the hybrid core are substantially disordered and wherein the hyvrid core has a chromatographically enhancing pore geometry (CEPG). In other embodiments, the inorganic portion of the hybrid core is present in an amount ranging from about 50 molar % to not more than about 75 molar %, wherein the pores of the hybrid core are substantially disordered and wherein the hyvrid core has a chromatographically enhancing pore geometry (CEPG). In yet other embodiments the inorganic portion of the hybrid core is present in an amount ranging from about 75 molar % to not more than about 100 molar %, wherein the pores of the hybrid core are substantially disordered and wherein the hyvrid core has a chromatographically enhancing pore geometry (CEPG).

In various embodiments of the aforementioned aspects of the invention, the amount of the inorganic portion of the hybrid core ranges from: about 25 molar % to not more than about 26 molar %; about 25 molar % to not more than about 27 molar %; about 25 molar % to not more than about 28 molar %; about 25 molar % to not more than about 29 molar %; about 25 molar % to not more than about 30 molar %; about 25 molar % to not more than about 31 molar %; about 25 molar % to not more than about 32 molar %; about 25 molar % to not more than about 33 molar %; about 25 molar % to not more than about 34 molar %; about 25 molar % to not more than about 35 molar %; about 25 molar % to not more than about 36 molar %; about 25 molar % to not more than about 37 molar %; about 25 molar % to not more than about 38 molar %; about 25 molar % to not more than about 39 molar %; about 25 molar % to not more than about 40 molar %; about 25 molar % to not more than about 41 molar %; about 25 molar % to not more than about 42 molar %; about 25 molar % to not more than about 43 molar %; about 25 molar % to not more than about 44 molar %; about 25 molar % to not more than about 45 molar % ; about 25 molar % to not more than about 46 molar % ; about 25 molar % to not more than about 47 molar %; about 25 molar % to not more than about 48 molar %; about 25 molar % to not more than about 49 molar %; about 25 molar % to not more than about 50 molar %; about 25 molar % to not more than about 100 molar %; about 50 molar % to not more than about 100 molar %; about 50 molar % to not more than about 75 molar %; and about 75 molar % to not more than about 100 molar %.

The inorganic portion of the hybrid core may be alumina, silica (SiC^), titanium oxide, zirconium oxide, or ceramic materials. The hybrid materials of the invention in which the inorganic portion is Siθ₂ is particularly advantageous. In certain embodiments, the core material may not be a hybrid core but may be an entirely inorganic core made only of an inorganic portion. In one embodiment, the organic content is from about 1 to about 40% carbon. In another embodiment, the organic content is from about 5 to about 35% carbon. In yet another embodiment, the invention provides a porous inorganic/organic hybrid particle, wherein the organic content is from about 25 to about 40% carbon. In a further embodiment, the organic content is from about 25 to about 35% carbon. In a further embodiment, the organic content is from about 5 to about 15% carbon.

In one embodiment, the hybrid material of the invention comprises a hybrid core of formula I: (SiO₂)_d/[R²((R)_p(R¹)_qSiO_t)_m] (I) wherein, R and R¹ are each independently Ci-Ci₈ alkoxy, CpCi₈ alkyl, CpCi₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, Cs-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, C₅-Ci₈ aryloxy, or CpCi₈ heteroaryl;

R² is CpCi₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, C₃-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, CpCi₈ heteroaryl; or absent; wherein each R² 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, R¹ and R² are optionally substituted; provided that: (1) when R² is absent, m=l and t = (4-(p+q)), when 0<p+q < 3; and

2

(2) when R² is present, m=2-20 and t = (3-(p+q)), when p+q < 2.

2

In certain embodiments, R² is absent, t=l .5 when p+q=l ; or t=l when p+q=2. In other embodiments, R is present, p=0, q is 0 or 1 and t=l .5 when q=0; or t=l when q=l .

In certain embodiments, R² is absent. In other embodiments, R² is present. In embodiments of formula I in which R is present, the invention comprises a hybrid core of formula I, wherein p is 0, q is 0, t is 1.5, m is 2, and R² is CpCi₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, C₃- Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, or CpCi₈ heteroaryl; wherein each R is attached to two or more silicon atoms. In a further embodiment, d is 0. In another embodiment, d is 0.11. In still another embodiment, d is 0.33. In certain embodiments, d is 0.83.

In other embodiments of formula I in which R² is present, the invention comprises a hybrid core of formula I, wherein d is 0, q is 0, and R is CpCi₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, C₃-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, or CpCi₈ heteroaryl; and wherein each R is attached to two or more silicon atoms. In a further embodiment, p is 0, 1, or 2. In another further embodiment, t is 1.0 or 1.5. In another embodiment, m is 1 or 2. Certain preferred embodiments of hybrid cores of formula I in which R is present are set forth in the following table (product numbers refer to the numbers used in the examples set forth below):

In another embodiment, the hybrid material of the invention comprises a hybrid core of formula II:

(SiO₂)_d/[(R)_p(R¹)_qSiO_t] (II) wherein,

R and R¹ are each independently C₁-C_1S alkoxy, C₁-C_1S alkyl, C₁-C_1S alkyl, C₂-C_1S alkenyl, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₁-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈ aryloxy, or C₁-C₁₈ heteroaryl; d is 0 to about 30; p and q are each independently 0.0 to 3.0, provided that when p+q=l then t=1.5; when p+q=2 then t=l ; or when p+q=3 then t=0.5.

In yet another embodiment, the hybrid material of the invention comprises a hybrid core of formula III: (SiO₂)_d/[R²((R¹)_rSiO_t)_m] (III) wherein,

R¹ is C₁-C₁₈ alkoxy, C₁-C₁₈ alkyl, C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₁-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈ aryloxy, or C₁-C₁₈ heteroaryl; R² is Ci-Ci₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, C₃-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, CpCi₈ heteroaryl; or absent; wherein each R 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=l .5; when r=l then t=l ; or when r=2, then t=0.5; and m is an integer from 1-20.

In various embodiments, the invention comprises a hybrid core of formulas I and II, wherein R is CpCi₈ alkoxy, CpCi₈ alkyl, or CpCi₈ alkyl. In various embodiments, the invention comprises a hybrid core of formulas I , II and III, wherein R¹ is CpCi₈ alkoxy, CpCi₈ alkyl, or CpCi₈ alkyl. In various embodiments, the invention comprises a hybrid core of formulas I and III, wherein R is CpCi₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, C₃-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, or CpCi₈ heteroaryl.

In yet another embodiment, the hybrid material of the invention comprises a hybrid core of 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; x and y are positive numbers, and z is a non negative number, wherein x +y + z = 1. In certain embodiments, 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. In a related embodiment, the hybrid material of the invention may comprise a hybrid core of 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 unit 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 (i.e., polymerizable) 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; x and y are positive numbers and z is a non negative number, wherein x +y + z = 1. In certain embodiments, 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. Repeat unit A may be derived from a variety of organic monomer reagents possessing one or more polymerizable moieties, capable of undergoing polymerization, e.g., a free radical- mediated polymerization. A monomers may be oligomerized or polymerized by a number of processes and mechanisms including, but not limited to, chain addition and step condensation processes, radical, anionic, cationic, ring-opening, group transfer, metathesis, and photochemical mechanisms.

A may also be one of the following:

wherein each R is independently H or a C₁ -C₁ Q alkyl group (e.g, methyl, ethyl, or propyl); m is an integer of from 1 to about 20; n is an integer of from 0 to 10; and Q is hydrogen, N(C^aIkVl)₃, N(Ci_₆alkyl)₂(Ci_₆alkyl-SO₃), or C(Ci_₆hydroxyalkyl)₃.

Repeat unit B may be derived from several mixed organic-inorganic monomer reagents possessing two or more different polymerizable moieties, capable of undergoing polymerization, e.g., a free radical-mediated (organic) and hydrolytic (inorganic) polymerization. B monomers may be oligomerized or polymerized by a number of processes and mechanisms including, but not limited to, chain addition and step condensation processes, radical, anionic, cationic, ring-opening, group transfer, metathesis, and photochemical mechanisms. B may also be one of the following:

Repeat unit C may be -Siθ2~ and may be derived from an alkoxysilane, such as tetraethoxysilane (TEOS) or tetramethoxysilane (TMOS).

In one embodiment, A is a substituted ethylene group, B is a oxysilyl-substituted alkyl group, and C is a oxysilyl group, for example the following:

A specific embodiment of a porous hybrid core of formula IV is:

wherein R₁ is H, F, Cl, Br, I, lower alkyl (e.g., CH₃ or CH₂CH₃);

R₂ and R₃ are each independently H, F, Cl, Br, I, alkane, substituted alkane, alkene, substituted alkene, aryl, substituted aryl, cyano, ether, substituted ether, embedded polar group;

R4 and R5 are each independently H, F, Cl, Br, I, alkane, substituted alkane, alkene, substituted alkene, aryl, substituted aryl, ether, substituted ether, cyano, amino, substituted amino, diol, nitro, sulfonic acid, cation or anion exchange groups,

0 < a < 2x, 0 < b < 4, and 0 < c < 4, provided that b + c < 4 when a = 1 ;

1 < d < 20,

0.0003 < y/z < 500 and 0.002 < x/(y+z) < 210.

In still another embodiment, the hybrid cores are spherical. In a further embodiment, the spherical core has a non-crystalline or amorphous molecular ordering. In a further embodiment, the spherical core has a non-periodic pore structure.

In other embodiments, the inorganic/organic hybrid core has a surface area of about 40 to

2 2

1100 m Ig. In certain instances, the hybrid core has a surface area of about 80 to 500 m Ig. In

2 other instances, the particle has a surface area of about 800 to 1100 m Ig. In one embodiment, the inorganic/organic hybrid core has micropore volumes of about

0.2 to 1.5 cm Ig. In certain instances, the hybrid core has micropore volumes of about 0.6 to 1.3 cm Ig.

In another embodiment, the inorganic/organic hybrid core has a micropore surface area of less than about 110 m /g. In certain instances, the hybrid core has a micropore surface area of less than about 105 m²/g. In other instances, the hybrid core has a micropore surface area of less than about 80 m Ig. In still other instances, the hybrid core has a micropore surface area of less than about 50 m²/g. In one embodiment, the porous inorganic/organic hybrid core has an average pore diameter of about 20 to lOOOA. In a further embodiment, the hybrid core has an average pore diameter of about 30 to 3OθA. In another embodiment, the hybrid core has an average pore diameter of about 60 to 2OθA. In a further embodiment, the particle has an average pore diameter of about 80 to l40A.

In another embodiment, the hybrid core has an average size of about 0.1 μm to about 300 μm. In a further embodiment, the hybrid core has an average size of about 0.1 μm to about 30 μm.

In certain embodiments, the hybrid core is hydro lyrically stable at a pH of about 1 to about 14. In one embodiment, the hybrid core is hydrolytically stable at a pH of about 10 to about 14. In another embodiment, the hybrid core is hydrolytically stable at a pH of about 1 to about 5.

In one embodiment, the invention comprises a inorganic/organic hybrid core as described herein, wherein the core is formed by hydro lytic condensation of one or more monomers selected from the group consisting of:

wherein R, R¹ and R² are as defined previously; X is CpCig alkoxy or CpCig alkyl; and n is 1-8. In a further embodiment, the monomer is 1 ,2-bis(triethoxysilyl)ethane:

In another further embodiment, the monomer is l,2-bis(methyldiethoxy silyl)ethane:

or 1,8- bis(triethoxysilyl)octane:

In other embodiment, the porous inorganic/organic hybrid core as described herein has been surface modified with a surface modifier having the formula Z_a(R')bSi-R", where Z = Cl, Br, I, Cl - C5 alkoxy, dialkylamino or trifluoromethanesulfonate; a and b are each an integer from 0 to 3 provided that a + b = 3; R' is a Cl - C6 straight, cyclic or branched alkyl group, and R" is a functionalizing group.

In another embodiment, the hybrid core have been surface modified by coating with a polymer.

In certain embodiments, R' is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, t-butyl, sec-butyl, pentyl, isopentyl, hexyl and cyclohexyl. In other embodiments, R is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, cyano, amino, diol, nitro, ester, a cation or anion exchange group, an alkyl or aryl group containing an embedded polar functionality and a chiral moiety.

In one embodiment, R" is a Cl - C30 alkyl group. In a further embodiment, R" comprises a chiral moiety. In another further embodiment, R" is a Cl - C20 alkyl group.

In certain embodiments, the surface modifier is selected from the group consisting of octyltrichlorosilane, octadecyltrichlorosilane, octyldimethylchlorosilane and octadecyldimethylchlorosilane. Preferably, the surface modifier is selected from the group consisting of octyltrichlorosilane and octadecyltrichlorosilane. In another embodiment, the hybrid core has been surface modified by a combination of organic group and silanol group modification.

In still another embodiment, the hybrid core has been surface modified by a combination of organic group modification and coating with a polymer. In a further embodiment, the organic group comprises a chiral moiety. In yet another embodiment, the hybrid core has been surface modified by a combination of silanol group modification and coating with a polymer.

In other embodiments, the hybrid core has been surface modified via formation of an organic covalent bond between the particle's organic group and the modifying reagent.

In still other embodiments, the hybrid core has been surface modified by a combination of organic group modification, silanol group modification and coating with a polymer.

In another embodiment, the hybrid core has been surface modified by silanol group modification. In another aspect, the porous inorganic/organic hybrid core has a chromatographically enhancing pore geometry, wherein the material comprises a combination of the particles described herein.

In certain embodiments, the porous inorganic/organic hybrid core is a monolith. In another aspect, the invention provides materials as described herein wherein the hybrid core further comprises a nanoparticle or a mixture of more than one nanoparticles dispersed within the hybrid core.

In certain embodiments, the nanoparticle is present in <20% by weight of the nanocomposite, <10% by weight of the nanocomposite, or <5% by weight of the nanocomposite. In other embodiments, the nanoparticle is crystalline or amorphous and may be silicon carbide, aluminum, diamond, cerium, carbon black, carbon nanotubes, zirconium, barium, cerium, cobalt, copper, europium, gadolinium, iron, nickel, samarium, silicon, silver, titanium, zinc, boron, oxides thereof, or a nitride thereof. In particular embodiments, the nanoparticle is a substance which comprises one or more moieties selected from the group consisting of nano- diamonds, silicon carbide, titanium dioxide, cubic-boronitride.

In other embodiments, the nanoparticles may be less than or equal to 200 nm in diameter, less than or equal to 100 nm in diameter, less than or equal to 50 nm in diameter, or less than or equal to 20 nm in diameter.

Surface Modification

The novel inorganic/organic hybrid materials of the invention may further be surface modified.

Thus, in one embodiment, the material as described herein may be surface modified with a surface modifier having the formula Z_a(R')bSi-R", where Z = Cl, Br, I, Cl - C5 alkoxy, dialkylamino or trifluoromethanesulfonate; a and b are each an integer from 0 to 3 provided that a + b = 3; R' is a Cl - Cβ straight, cyclic or branched alkyl group, and R" is a functionalizing group.

In another embodiment, the materials have been surface modified by coating with a polymer. In certain embodiments, R' is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, t-butyl, sec-butyl, pentyl, isopentyl, hexyl and cyclohexyl. In other embodiments, R is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, cyano, amino, diol, nitro, ester, a cation or anion exchange group, an alkyl or aryl group containing an embedded polar functionality and a chiral moiety. In one embodiment, R" is a Cl - C30 alkyl group. In a further embodiment, R" comprises a chiral moiety. In another further embodiment, R" is a Cl - C20 alkyl group.

In certain embodiments, the surface modifier is selected from the group consisting of octyltrichlorosilane, octadecyltrichlorosilane, octyldimethylchlorosilane and octadecyldimethylchlorosilane. In some embodiments, the surface modifier is selected from the group consisting of octyltrichlorosilane and octadecyltrichlorosilane. In other embodiments, the surface modifier is selected from the group consisting of an isocyanate or 1,1'- carbonyldiimidazole (particularly when the hybrid group contains a (CH₂)3θH group).

In another embodiment, the material has been surface modified by a combination of organic group and silanol group modification.

In still another embodiment, the material has been surface modified by a combination of organic group modification and coating with a polymer. In a further embodiment, the organic group comprises a chiral moiety.

In yet another embodiment, the material has been surface modified by a combination of silanol group modification and coating with a polymer.

In other embodiments, the material has been surface modified via formation of an organic covalent bond between the particle's organic group and the modifying reagent.

In still other embodiments, the material has been surface modified by a combination of organic group modification, silanol group modification and coating with a polymer. In another embodiment, the material has been surface modified by silanol group modification.

In certain embodiments, the surface modified layer may be porous or nonporous.

Separation Devices and Kits Another aspect provides a variety of separations devices having a stationary phase comprising the inorganic/organic hybrid materials as described herein. The separations devices include, e.g., chromatographic columns, thin layer plates, filtration membranes, sample cleanup devices and microtiter plates. The separations devices can be used for a variety of separations techniques including, but not limited to, normal-phase separations, reversed-phase separations, HILIC separations, SFC separations, affinity separations, and SEC separations.

The inorganic/organic hybrid materials impart to these devices improved lifetimes because of their improved stability. Thus, in a particular aspect, the invention provides a chromatographic column having improved lifetime, comprising a) a column having a cylindrical interior for accepting a packing material, and b) a packed chromatographic bed comprising the inorganic/organic hybrid materials as described herein.

The invention also provides for a kit comprising the inorganic/organic hybrid materials as described herein, as described herein, and instructions for use. In one embodiment, the instructions are for use with a separations device, e.g., chromatographic columns, thin layer plates, filtration membranes, sample cleanup devices and microtiter plates.

Synthesis of Materials of the Invention

The invention also provides methods for producing the inorganic/organic hybrid materials described herein.

In one embodiment, the invention provides a method for producing the inorganic/organic hybrid materials described herein comprising: providing a hybrid core material; and condensing one or more polymeric organofunctional metal precursors, and/or polymeric metal oxide precursors on the surface of the hybrid core .

In another embodiment, the invention provides a method for producing the inorganic/organic hybrid materials described herein comprising: providing a hybrid core material; applying a 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 on the surface of the hybrid core; and further condensing said surface.

In certain embodiments, the method producing the inorganic/organic hybrid materials described herein further comprises the step of subjecting the hybrid material to hydrothermal treatment.

In another embodiment, the invention provides a method for producing the inorganic/organic hybrid materials described herein, comprising the steps of: providing a hybrid core material; and condensing one or more polymeric organofunctional metal precursors, and/or polymeric metal oxide precursors on the surface of the hybrid core.

In another embodiment, the invention provides a method for producing the inorganic/organic hybrid materials described herein comprising the steps of: providing a hybrid core material; applying a 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 on the surface of the hybrid core; and further condensing said surface. In certain embodiments, the process of producing the inorganic/organic hybrid materials described herein as described above further comprises the step of subjecting the hybrid material to hydrothermal treatment.

In a particular embodiment, the invention provides methods for producing the inorganic/organic hybrid materials described herein in which the hybrid core of the materials is provided by the steps of: a) hydro lytically condensing one or more monomers selected from the group consisting of organoalkoxysilanes and tetraalkoxysilanes with one or more monomers selected from the group consisting of organoalkoxysilanes, tetraalkoxysilanes, metal oxide precursors, and ceramic precursors to produce a polyorganoalkoxysiloxane; b) further condensing the polyorganoalkoxysiloxane to form a spherical porous particle; and c) subjecting the resulting particle to hydrothermal treatment.

In an embodiment of the foregoing method when preparing a hybrid core, comprising the inorganic portion in an amount ranging from about 0 molar % to not more than about 25 molar %, wherein the pores of the particle are substantially disordered, the hydro lytic condensing of one or more monomers excludes tetraalkoxysilanes. In some embodiments of the foregoing method, the inorganic portion is present in an amount ranging from about 0 molar % to not more than about 100 molar %; from 25 molar % to about 50 molar %, from about 50 molar % to about 75 molar %; or from about 75 molar % to about 100 molar %; wherein the pores of the particle are substantially disordered, the hydrolytic condensing of one or more monomers excludes tetraalkoxysilanes .

In one embodiment, the metal oxide precursors of the hybrid cores are selected from the group consisting of the oxide, hydroxide, ethoxide, methoxide, propoxide, isopropoxide, butoxide, sec-butoxide, tert-butoxide, iso-butoxide, phenoxide, ethylhexyloxide, 2-methyl-2-butoxide, nonyloxide, isooctyloxide, glycolates, carboxylate, nitrate, chlorides, and mixtures thereof of titanium, zirconium, or aluminum. Preferably, the metal oxide precursors are methyl titanium triisopropoxide, methyl titanium triphenoxide, titanium allylacetoacetatetriisopropoxide, titanium methacrylate triisopropoxide, titanium methacryloxyethylacetoacetate triisopropoxide, pentamethylcyclopentadienyl titanium trimethoxide, pentamethylcyclopentadienyl titanium trichloride, and zirconium methacryloxyethylacetoacetate tri-n-propoxide.

In another aspect, the invention provides methods for producing the materials of the invention in which the hybrid core of the materials is provided by the steps of: a) hydrolytically condensing one or more monomers selected from the group consisting of organoalkoxysilanes and tetraalkoxysilanes, to produce a polyorganoalkoxysiloxane; b) further condensing the polyorganoalkoxysiloxane to form a spherical porous particle; and c) subjecting the resulting particle to hydrothermal treatment; to thereby produce a porous inorganic/organic hybrid core .

In certain embodiments, the invention provides a method of producing a hybrid core comprising Siθ₂ in an amount ranging from about 0 molar % to not more than about 25 molar %, wherein the pores of the particle are substantially disordered, wherein the one or more monomers exclude tetraalkoxysilanes. In some embodiments of the foregoing method Siθ₂ is present in an amount ranging from about 0 molar % to not more than about 100 molar %; from 25 molar % to about 50 molar %, from about 50 molar % to about 75 molar %; or from about 75 molar % to about 100 molar %; wherein the pores of the particle are substantially disordered, wherein the one or more monomers exclude tetraalkoxysilanes.

In still another aspect, the invention provides methods for producing the materials of the invention in which a hybrid core, comprising Siθ₂ in an amount ranging from about 0 molar % to not more than about 100 molar %, wherein the pores of the particle are substantially disordered, is provided by the steps of: a) hydrolytically condensing one or more monomers selected from the group consisting of organoalkoxysilanes and tetraalkoxysilanes, to produce a polyorganoalkoxysiloxane; b) further condensing the polyorganoalkoxysiloxane to form a spherical porous particle; and c) subjecting the resulting particle to hydrothermal treatment; to thereby produce a porous inorganic/organic hybrid particle of the invention.

In certain embodiments, the condensing step comprises treating an aqueous emulsion of the polyorganoalkoxysiloxane with base to form a spherical core.

In another embodiment, the invention provides a method of producing a porous inorganic/organic hybrid core as described above, further comprising treating the spherical porous particle with acid.

In still another embodiment, the invention provides a method of producing a porous inorganic/organic hybrid core as described above, further comprising treating the aqueous emulsion of the polyorganoalkoxysiloxane with one or more additional aliquots of base to form a spherical particle. In a further embodiment, the invention provides a method further comprising treating the spherical porous particle with acid.

In certain embodiments, the invention provides a method, wherein the hybrid core has a chromatographically enhancing pore geometry (CEPG).

In one embodiment, the foregoing methods produce the porous inorganic/organic hybrid core having formula I, II, or II described above.

In certain embodiments, the invention provides a method, further comprising preparing an aqueous suspension of the polyorganoalkoxysiloxane and gelling in the presence of a base catalyst to produce the porous inorganic/organic hybrid core.

In certain embodiments of the method of producing the hybrid core, step a) or step b) is acid-catalyzed or base-catalyzed. In one embodiment, step a) is acid catalyzed. In another embodiment, step b) is base catalyzed. In a further embodiment, the base-catalyzed reaction is an oil-in- water emulsification reaction. Thus, in an advantageous embodiment, step b) of producing the hybrid core further comprises treating an aqueous emulsion of the polyorganoalkoxysiloxane with base. In a further advantageous embodiment, following treatment with base, the particle produced in step b) is treated with acid. In an alternative advantageous embodiment, the treatment of the aqueous emulsion of the polyorganoalkoxysiloxane with base in step b) is followed by treatment with one or more additional aliquots of base and then the resulting particles are treated with acid.

Suitable acids for use with the methods of the invention include hydrochloric acid, hydrobromic acid, hydrofluoric acid, hydroiodic acid, sulfuric acid, formic acid, acetic acid, trichloroacetic acid, trifluoroacetic acid and phosphoric acid. Suitable bases for use with the methods of the invention include alkyl amines, ammonium hydroxide, hydroxide salts of the group I and group II metals, carbonate and hydrogen carbonate salts of the group I metals and alkoxide salts of the group I and group II metals. Alkyl amines include, e.g., trimethyl amine, triethyl amine, diisopropyl ethyl amine, etc. Tris(hydroxymethyl) methylamine is a preferred alkyl amine.

In certain embodiments, steps a) and b) of producing the hybrid core are performed in a solvent selected from the group consisting of water, methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, pentanol, hexanol, cyclohexanol, hexafluoroisopropanol, cyclohexane, petroleum ethers, diethyl ether, dialkyl ethers, tetrahydrofuran, acetonitrile, ethyl acetate, pentane, hexane, heptane, benzene, toluene, xylene, N,N-dimethylformamide, dimethyl sulfoxide, 1-methyl- 2-pyrrolidinone, methylene chloride, chloroform and combinations thereof. In still another aspect, the invention provides methods for producing the inorganic/organic hybrid materials described herein in which a hybrid core, of formula IV or formula V, is produced comprising the steps of:

(b) copolymerizing the product of step (a) with an organic olefin monomer; and

(c) further condensing the product of step (b) to form a spherical porous particle. In still another aspect, the invention provides methods for producing the materials of the invention in which a hybrid core, of formula IV or formula V described above, is produced comprising the steps of:

(a) copolymerizing an organic olefin monomer with an alkenyl-functionalized organosilane; and

(b) hydrolytically condensing the product of step (a) with a tetraalkoxysilane in the presence of a non-optically active porogen; and (c) further condensing the product of step (b) to form a spherical porous particle.

In certain embodiments, the copolymerizing step is free radical-initiated and wherein the hydrolytically condensing step is an acid- or base-catalyzed.

In one embodiment, the invention provides a method as described above, further comprising subjecting the resulting hybrid core to hydrothermal treatment. In certain embodiments, the spherical hybrid core produced in step b) or step c) are sized to generate a particle size distribution that is distinct from the particle size distribution of the spherical porous particles produced in step b) or step c).

In other embodiments, the spherical hybrid core has a non-crystalline or amorphous molecular ordering. In a further embodiment, the spherical hybrid core has a non-periodic pore structure.

In certain embodiments, the invention provides a method of producing the hybrid core of the material of the invention, wherein the hybrid core has a surface area of about 40 to 1100

2 2 m Ig. In a further embodiment, the hybrid core has a surface area of about 80 to 500 m Ig. In

2 another further embodiment, the hybrid core has a surface area of about 800 to 1100 m Ig. In one embodiment, the invention provides a method of producing the hybrid core of the material of the invention wherein the hybrid core has micropore volumes of about 0.2 to 1.5

3 cm Ig. In a further embodiment, the hybrid core has micropore volumes of about 0.6 to 1.3 cm Ig.

In another embodiment, the invention provides a method of producing the hybrid core of the material of the invention wherein the hybrid core has a micropore surface area of less than about 110 m²/g. In a further embodiment, the hybrid core has a micropore surface area of less than about 105 m /g. In another embodiment, the hybrid core has a micropore surface area of less than about 80 m²/g. In a further embodiment, the hybrid core has a micropore surface area of less than about 50 m /g. In another embodiment, the invention provides a method of producing the hybrid core of the material of the invention wherein the hybrid core has an average pore diameter of about 20 to 5OθA. In a further embodiment, the hybrid core has an average pore diameter of about 30 to 180A.

In certain instances, the hybrid core of the material has an average pore diameter of about 60 to 2OθA. Preferably, the hybrid core has an average pore diameter of about 80 to 14θA.

In other instances, the hybrid core of the material has an average size of about 0.1 μm to about 300 μm, preferably about 0.1 μm to about 30 μm.

In another embodiment, the invention provides a method of producing the hybrid core of the material of the invention wherein the hybrid core is hydro lytically stable at a pH of about 1 to about 14. In certain instances, the hybrid core is hydro lytically stable at a pH of about 10 to about 14. In other instances, the particle is hydrolytically stable at a pH of about 1 to about 5.

In one embodiment, the invention provides a method of producing the hybrid core of the material of the invention wherein the organic content is from about 25 to about 40% carbon. In a further embodiment, the organic content is from about 25 to about 35% carbon. In one embodiment, the organic content is from about 1 to about 40% carbon. In another embodiment, the organic content is from about 5 to about 35% carbon. In yet another embodiment, the invention provides a porous inorganic/organic hybrid particle, wherein the organic content is from about 25 to about 40% carbon. In a further embodiment, the organic content is from about 25 to about 35% carbon. In a further embodiment, the organic content is from about 5 to about 15% carbon.

In certain instances, the invention provides a method of producing the hybrid core of the material of the invention wherein R is CpCi₈ alkoxy, CpCi₈ alkyl, or CpCi₈ alkyl.

In another embodiment, R¹ is CpCi₈ alkoxy CpCi₈ alkyl, or CpCi₈ alkyl.

In other embodiments, R² is Ci-Cig alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, C₃-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, or CpCi₈ heteroaryl.

In one embodiment, the invention provides a method of producing the hybrid core of formula I wherein p is 0, q is 0, t is 1.5, m is 2, and R is CpCi₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, C₃-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, or CpCi₈ heteroaryl; wherein each R is attached to two or more silicon atoms. In a further embodiment, d is 0. In another further embodiment, d is 0.11. In still another further embodiment, d is 0.33. In yet another further embodiment, d is 0.83.

In another embodiment, the invention provides a method of producing the hybrid core of formula I wherein d is 0, q is 0, and R is CpCi₈ alkyl, C₂-C₁8 alkenyl, C₂-C₁8 alkynyl, C3-C₁8 cycloalkyl, Ci-Ci₈ heterocycloalkyl, C₅-Ci₈ aryl, or CpCi₈ heteroaryl; wherein each R² is attached to two or more silicon atoms. In a further embodiment, p is 0, 1, or 2. In another embodiment, t is 1.0 or 1.5. In another embodiment, m is 1 or 2.

In one embodiment, the invention provides a method of producing the hybrid core of the invention wherein the one or more monomers are selected from the group consisting of:

wherein R, R¹ and R² are as defined previously; X is CpCi₈ alkoxy or CpCi₈ alkyl; and n is 1-8. In certain embodiments, the monomer is l,2-bis(triethoxysilyl)ethane:

In other embodiments, the monomer is l,2-bis(methyldiethoxy silyl)ethane:

or 1,8- bis(triethoxysilyl)octane:

The freshmade hybrid cores resulting from step b) are advantageously sized to generate a particle size distribution that is distinct from the particle size distribution of the freshmade spherical porous particles resulting form step b). Any number of well known sizing techniques may be used. Such sizing techniques are described, for example, in W. Gerhartz, et al. (editors) Ullmann's Encyclopedia of Industrial Chemistry, 5^th edition, Volume B2: Unit Operations I, VCH Verlagsgesellschaft mbH, (Weinheim , Fed. Rep. Germ. 1988). Particles are advantageously sized to a diameter range of about 0.5 μm to about 300 μm, more advantageously about 1 μm to about 20 μm.

The hybrid cores of the material of the invention can be prepared by the foregoing methods. Further details on the synthesis of the hybrid cores of formulas IV and V can be found, for example, in WO2004/041398-A2. Certain embodiments of the synthesis of the porous inorganic/organic hybrid particles of formulas I-III described above are further described as follows.

Porous spherical particles of hybrid core may, in a preferred embodiment, be prepared by a four-step process. In the first step, an organoalkoxysilane can be prepolymerized by itself, or with one or more organoalkoxysilanes or with 0-49 molar % tetraalkoxysilane such as tetraethoxysilane (TEOS) to form a polyorganoalkoxysiloxe (POS) by co-hydrolyzing in the presence of an acid catalyst. A list of organoalkoxysilanes that may be used in this approach includes (but is not limited to); bis(triethoxysilyl)ethane; bis(triethoxylsilyl)octane; bis(methyldiethoxysilyl)ethane; bis(triethoxysilyl)ethene; bis(trimethoxysilylethyl)benzene; ethyltriethoxysilane; diethyldiethoxysilane; mercaptopropyltriethoxysilane; methyltriethoxysilane; vinyltriethoxysilane; hexyltriethoxysilane; chloropropyltriethoxysilane; phenylethyltrimethoxysilane; octadecyltrimethoxysilane; octyltrimethoxysilane; 3,3.3- trifluoropropyltrimethoxysilane; and 3-cyanobutyltriethoxysilane. The use of reactive organoalkoxysilanes that have been shown to react by protodesilylation, deprotection, or decompose may also be useful in introducing porosity into hybrid particles. A list of organoalkoxysilanes that may protodesilylate, deprotect or decompose to introduce porosity into hybrid cores includes (but is not limited to); phenyltriethoxysilane; methacryloxypropyltrimethoxysilane; acetyloxyethyltrimethoxysilane, chloroethyltriethoxysilane, and fluorotriethoxysilane.

In the second step, the POS is suspended in an aqueous medium in the presence of a surfactant or a combination of surfactants and gelled into porous spherical hybrid cores. The process of gelation can be controlled using a single addition of base catalyst or multiple additions of base catalyst, a combination of base and acid catalyst, or the multi-addition of base catalyst followed by acid catalyst.

In the third step, the pore structure of the hybrid cores is modified by hydrothermal treatment, producing an intermediate hybrid product which may be used for particular purposes itself, or may be further processed below. The above three steps of the process allow much better control of the particle sphericity, morphology, pore volume and pore sizes than those described in the prior art, and thus provide the chromatography-enhancing pre geometry. In one embodiment of the invention, the surface organic groups of the hybrid cores and/or the materials may be derivatized or modified in a subsequent step via formation of an organic covalent bond between the particle's organic group and the modifying reagent. Alternatively, the surface silanol groups of the hybrid cores and/or the surrounding material materials are derivatized or modified into siloxane functional groups, such as by reacting with an organotrihalosilane, e.g., octadecyltrichlorosilane, or a halopolyorganosilane, e.g., octadecyldimethylchlorosilane. Alternatively, the surface organic and silanol groups of the hybrid cores and/or the surrounding material materials are both derivatized or modified. The surface of the thus-prepared material is then covered by the organic groups, e.g., alkyl, embedded during the gelation and the organic groups added during the derivatization process or processes. The surface coverage by the overall organic groups is higher than in conventional silica-based packing materials and, therefore, the surface concentration of the remaining silanol groups in the hybrid particles is smaller. The resulting material, used as a stationary phase for LC, shows excellent peak shape for basic analytes and better stability to alkaline mobile phases than silica-based packing materials.

Where the prepolymerization step involves co-hydrolyzing a mixture of the two or more components in the presence of an acid catalyst, the content of the organoalkoxysilane, e.g., organotrialkoxysilane can be varied, e.g., from about 0.03 to about 1.0 mole per mole, or more preferably, about 0.2 to about 0.5 mole per mole, of the tetraalkoxysilane. The amount of the water used for the hydrolysis can be varied, e.g., from l.lO to 1.35 mole per mole of the silane. The silane, water and the ethanol mixture, in the form of a homogeneous solution, is stirred and heated to reflux under a flow of argon. After it is refluxed for a time sufficient to prepolymerize to form polyorganoalkoxysiloxane (POS), e.g., polyalkylalkoxysiloxane, the solvent and the side product, mainly ethanol, is distilled off from the reaction mixture. Thereafter, the residue is heated at an elevated temperature, e.g., in the range of 45 to 85°C under an atmosphere of an inert gas, e.g., nitrogen, argon, etc., for a period of time, e.g., 0.5 to 48 h. The residue is further heated at 95°C to 120⁰C , e.g., for 1 to 3 h at atmospheric pressure or under reduced pressure, e.g., 10

2 -3 - 10 torr, to remove any volatile species.

In the second step, the POS is suspended into fine beads in a solution containing water and an alcohol, such as ethanol or butanol, at 55°C by agitation. The volume percent of alcohol in the solution is varied from 10 to 20%. A surfactant such Triton" X-100, Triton" X- 165, as sodium dodecylsulfate (SDS), ammonia docecylsulfate or TRIS docecylsulfate, is added into the suspension as the suspending agent. The surfactants, are believed to be able to orient at the hydrophobic/hydrophilic interface between the POS beads and the aqueous phase to stabilize the POS beads. The surfactants are also believed to enhance the concentration of water and the base catalyst on the surface of the POS beads during the gelation step, through their hydrophilic groups, which induces the gelling of the POS beads from the surface towards the center. Use of surfactants to modulate the surface structure of the POS beads stabilizes the shape of the POS beads throughout the gelling process and minimizes or suppresses formation of particles having an irregular shapes, e.g., "shell shaped", and inhomogeneous morphology.

It is also possible to suspend a solution containing POS and a porogen in the aqueous phase, instead of POS alone. The porogen, which is insoluble in the aqueous phase, remains in the POS beads during the gelation step and functions as a porogen. Porogen include, e.g., toluene and mesitylene. By controlling the relative amount of toluene in the POS/toluene solution, the pore volume of the final hybrid particles can be more precisely controlled. This allows the preparation of hybrid particles having large pore volume, e.g., 0.25-1.5 cffiVg.

The gelation step is initiated by adding the basic catalyst, e.g., ammonium hydroxide into the POS suspension. Thereafter, the reaction mixture is agitated to drive the reaction to completion. Ammonium hydroxide and sodium hydroxide are preferred. The particles are isolated and washed with water. The condensation can be furthered by redispersing the particles in an aqueous acid suspension at reflux for 1-4 days. The use of hydrochloric acid is preferred. The thus-prepared freshmade hybrid cores and/or surrounding material materials are filtered and washed with water and methanol free of ammonium ions, then dried.

In one embodiment, the pore structure of the as-prepared hybrid cores and/or surrounding material materials is modified by hydrothermal treatment, which enlarges the openings of the pores as well as the pore diameters, as confirmed by nitrogen (N 2) sorption analysis. The hydrothermal treatment is performed by preparing a slurry containing the as-prepared hybrid material and a solution of a base in water, heating the slurry in an autoclave at an elevated temperature, e.g., 100 to 200⁰C, for a period of 10 to 30 h. The use of an alkyl amine such as trimethylamine (TEA) or Tris(hydroxymethyl) methyl amine or the use of sodium hydroxide is advantageous. The thus-treated hybrid material is cooled, filtered and washed with water and methanol, then dried at 8O⁰C under reduced pressure for 16 h.

In certain embodiments, following hydrothermal treatment, the surfaces of the hybrid cores and/or the materials are modified with various agents. Such "surface modifiers" include (typically) organic functional groups which impart a certain chromatographic functionality to a chromatographic stationary phase. The porous inorganic/organic hybrid particles possess both organic groups and silanol groups which may additionally be substituted or derivatized with a surface modifier.

The surface of the hydrothermally treated hybrid cores and/or surrounding material materials contains organic groups, which can be derivatized by reacting with a reagent that is reactive towards the particles' organic group. For example, vinyl groups on the particle can be reacted with a variety of olefin reactive reagents such as bromine (Br₂), hydrogen (H₂), free radicals, propagating polymer radical centers, dienes and the like. In another example, hydroxyl groups on the particle can be reacted with a variety of alcohol reactive reagents such as isocyanates, carboxylic acids, carboxylic acid chlorides and reactive organosilanes as described below. Reactions of this type are well known in the literature, see, e.g., March, J. Advanced Organic Chemistry, 3^rd Edition, Wiley, New York, 1985; Odian, G. The Principles of Polymerization, 2^nd Edition, Wiley, New York, 1981.

In addition, the surface of the hydrothermally treated hybrid cores and/or surrounding material materials also contains silanol groups, which can be derivatized by reacting with a reactive organosilane. The surface derivatization of the hybrid cores and/or surrounding material materials is conducted according to standard methods, for example by reaction with octadecyltrichlorosilane or octadecyldimethylchlorosilane in an organic solvent under reflux conditions. An organic solvent such as toluene is typically used for this reaction. An organic base such as pyridine or imidazole is added to the reaction mixture to catalyze the reaction. The product of this reaction is then washed with water, toluene and acetone and dried at 80⁰C to 100⁰C under reduced pressure for 16 h. The resultant hybrid particles can be further reacted with a short-chain silane such as trimethylchlorosilane to endcap the remaining silanol groups, by using a similar procedure described above. Surface modifiers such as disclosed herein are attached to the base material, e.g., via derivatization or coating and later crosslinking, imparting the chemical character of the surface modifier to the base material. In one embodiment, the organic groups of the hybrid cores and/or surrounding material materials react to form an organic covalent bond with a surface modifier. The modifiers can form an organic covalent bond to the particle's organic group via a number of mechanisms well known in organic and polymer chemistry including but not limited to nucleophilic, electrophilic, cycloaddition, free-radical, carbene, nitrene and carbocation reactions. Organic covalent bonds are defined to involve the formation of a covalent bond between the common elements of organic chemistry including but not limited to hydrogen, boron, carbon, nitrogen, oxygen, silicon, phosphorus, sulfur and the halogens. In addition, carbon-silicon and carbon-oxygen-silicon bonds are defined as organic covalent bonds, whereas silicon-oxygen- silicon bonds that are not defined as organic covalent bonds.

The term "functionalizing group" includes organic functional groups which impart a certain chromatographic functionality to a chromatographic stationary phase, including, e.g., octadecyl (Ci 8) or phenyl. Such functionalizing groups are incorporated into base material directly, or present in, e.g., surface modifiers such as disclosed herein which are attached to the base material, e.g., via derivatization or coating and later crosslinking, imparting the chemical character of the surface modifier to the base material.

In certain embodiments, silanol groups are surface modified. In other embodiments, organic groups are surface modified. In still other embodiments, the hybrid cores' and/or surrounding material materials' organic groups and silanol groups are both surface modified or derivatized. In another embodiment, the particles are surface modified by coating with a polymer. In certain embodiments, surface modification by coating with a polymer is used in conjunction with silanol group modification, organic group modification, or both silanol and organic group modification. More generally, the surface of hybrid cores and/or surrounding material materials may be modified by: treatment with surface modifiers including compounds of formula Z_a(R')bSi-R", where Z = Cl, Br, I, Cl - C5 alkoxy, dialkylamino, e.g., dimethylamino, or trifluoromethanesulfonate; a and b are each an integer from 0 to 3 provided that a + b = 3; R' is a Cl - Cβ straight, cyclic or branched alkyl group, and R" is a functionalizing group. In certain instances, such particles have been surface modified by coating with a polymer.

R' includes, e.g., methyl, ethyl, propyl, isopropyl, butyl, t-butyl, sec-butyl, pentyl, isopentyl, hexyl or cyclohexyl; preferably, R' is methyl.

The functionalizing group R" may include alkyl, alkenyl, alkynyl, aryl, cyano, amino, diol, nitro, ester, cation or anion exchange groups, an alkyl or aryl group containing an embedded polar functionalities or chiral moieties. Examples of suitable R" functionalizing groups include chiral moieties, C1-C30 alkyl, including C1-C20, such as octyl (C8), octadecyl (C 18) and triacontyl (C30); alkaryl, e.g., Ci-C4-phenyl; cyanoalkyl groups, e.g., cyanopropyl; diol groups, e.g., propyldiol; amino groups, e.g., aminopropyl; and alkyl or aryl groups with embedded polar functionalities, e.g., carbamate functionalities such as disclosed in U. S. Patent No. 5,374,755, and chiral moieties. Such groups include those of the general formula

wherein 1, m, 0, r and s are 0 or 1 , n is 0, 1 , 2 or 3 p is 0, 1 , 2, 3 or 4 and q is an integer from 0 to 19; R3 is selected from the group consisting of hydrogen, alkyl, cyano and phenyl; and Z, R', a and b are defined as above. Preferably, the carbamate functionality has the general structure indicated below:

wherein R may be, e.g., cyanoalkyl, t-butyl, butyl, octyl, dodecyl, tetradecyl, octadecyl, or benzyl. Advantageously, R is octyl, dodecyl, or octadecyl.

In certain applications, such as chiral separations, the inclusion of a chiral moiety as a functionalizing group is particularly advantageous.

Polymer coatings are known in the literature and may be provided generally by polymerization or polycondensation of physisorbed monomers onto the surface without chemical bonding of the polymer layer to the support (type I), polymerization or polycondensation of physisorbed monomers onto the surface with chemical bonding of the polymer layer to the support (type II), immobilization of physisorbed prepolymers to the support (type III) and chemisorption of presynthesized polymers onto the surface of the support (type IV). see, e.g., Hanson, et al. , J. Chromat. A656 (1993) 369-380, the text of which is incorporated herein by reference. As noted above, coating the hybrid material with a polymer may be used in conjunction with various surface modifications described in the invention.

Thus, in certain embodiments, the surface modifier is selected from the group consisting of octyltrichlorosilane, octadecyltrichlorosilane, octyldimethylchlorosilane and octadecyldimethylchlorosilane. In a further embodiment, the surface modifier is selected from the group consisting of octyltrichlorosilane and octadecyltrichlorosilane.

In another embodiment, the hybrid cores and/or surrounding material materials have been surface modified by a combination of organic group and silanol group modification.

In other embodiments, the hybrid cores and/or surrounding material materials have been surface modified by a combination of organic group modification and coating with a polymer. In other embodiments, the hybrid cores and/or surrounding material materials have been surface modified by a combination of silanol group modification and coating with a polymer.

In another embodiment, the hybrid cores and/or surrounding material materials have been surface modified via formation of an organic covalent bond between the hybrid cores' and/or surrounding material materials' organic group and the modifying reagent. In certain embodiments, the hybrid cores and/or surrounding material materials have been surface modified by a combination of organic group modification, silanol group modification and coating with a polymer. In one embodiment, the hybrid cores and/or surrounding material materials have been surface modified by silanol group modification.

In another embodiment, the invention provides a method wherein the hybrid cores and/or surrounding material materials are modified by further including a porogen. In a further embodiment, the porogen is selected from the group consisting of cyclohexanol, toluene, mesitylene, 2-ethylhexanoic acid, dibutylphthalate, 1 -methyl-2-pyrrolidinone, 1 -dodecanol and Triton X-45. In certain embodiments, the porogen is toluene or mesitylene.

In one embodiment, the invention provides a method wherein the hybrid cores and/or surrounding material materials are further modified by including a surfactant or stabilizer. In certain embodiments, the surfactant is Triton X-45, Triton XlOO, Triton X305, TLS, Pluronic F- 87, Pluronic P-105, Pluronic P-123, sodium dodecylsulfate (SDS), ammonia docecylsulfate, TRIS docecylsulfate, or Triton X-165. In certain embodiments, the surfactant is sodium dodecylsulfate (SDS), ammonia docecylsulfate, or TRIS docecylsulfate.

Certain embodiments of the synthesis of the hybrid cores and/or surrounding material materials described above are further illustrated in the Examples below.

Examples

The present invention may be further illustrated by the following non-limiting examples describing the preparation of porous inorganic/organic hybrid particles and their use.

Materials

All reagents were used as received unless otherwise noted. Those skilled in the art will recognize that equivalents of the following supplies and suppliers exist and, as such, the suppliers listed below are not to be construed as limiting.

Characterization

Those skilled in the art will recognize that equivalents of the following instruments and suppliers exist and, as such, the instruments listed below are not to be construed as limiting. The %C values were measured by combustion analysis (CE-440 Elemental Analyzer;

Exeter Analytical Inc., North Chelmsford, MA) or by Coulometric Carbon Analyzer (modules CM5300, CM5014, UIC Inc., Joliet, IL). The specific surface areas (SSA), specific pore volumes (SPV) and the average pore diameters (APD) of these materials were measured using the multi-point N2 sorption method (Micromeritics ASAP 2400; Micromeritics Instruments Inc., Norcross, GA). The SSA was calculated using the BET method, the SPV was the single point value determined for P/P_o > 0.98 and the APD was calculated from the desorption leg of the isotherm using the BJH method. The micropore surface area (MSA) was determined as the cumulative adsorption pore diameter data for pores < 34 A subtracted from the specific surface area (SSA). The median mesopore diameter (MPD) and mesopore pore volume (MPV) were measured by mercury porosimetry (Micromeritics AutoPore IV, Micromeritics, Norcross, GA). Skeletal densities were measured using a Micromeritics AccuPyc 1330 Helium Pycnometer (V2.04N, Norcross, GA). Scanning electron microscopic (SEM) image analyses were performed (JEOL JSM-5600 instrument, Tokyo, Japan) at 7 kV. High resolution SEM image analyses were performed using a Focused Ion Beam (FIB/SEM) instrument (Helios 600 Nanolab, FEI Company, Hillsboro, OR) at 20 kV. Particle sizes were measured using a Beckman Coulter

Multisizer 3 analyzer (30-μm aperture, 70,000 counts; Miami, FL). The particle diameter (dp) was measured as the 50% cumulative diameter of the volume based particle size distribution. The width of the distribution was measured as the 90% cumulative volume diameter divided by the 10% cumulative volume diameter (denoted 90/10 ratio). Viscosity was determined for these materials using a Brookfield digital viscometer Model DV-II (Middleboro, MA). FT-IR spectra were obtained using a Bruker Optics Tensor 27 (Ettlingen, Germany). Multinuclear (¹³C, ²⁹Si) CP-MAS NMR spectra were obtained using a Bruker Instruments Avance-300 spectrometer (7 mm double broadband probe). The spinning speed was typically 5.0-6.5 kHz, recycle delay was 5 sec. and the cross-polarization contact time was 6 msec. Reported ¹³C and ²⁹Si CP-MAS NMR spectral shifts were recorded relative to tetramethylsilane using the external standards adamantane (¹³C CP-MAS NMR, δ 38.55) and hexamethylcyclotrisiloxane (²⁹Si CP-MAS NMR, δ -9.62). Populations of different silicon environments were evaluated by spectral deconvolution using DMFit software. [Massiot, D.; Fayon, F.; Capron, M.; King, L; Le Calve, S.; Alonso, B.; Durand, J.-O.; Bujoli, B.; Gan, Z.; Hoatson, G. Magn. Reson. Chem. 2002, 40, 70-76]

EXAMPLE 1

Synthesis of Polyorganosiloxanes.

One or more tetraalkoxysilanes or organoalkoxysilanes (all from Gelest Inc., Morrisville, PA or United Chemical Technologies, INC., Bristol, PA) or zirconium n-propoxide (70% in propanol, Gelest Inc., Morrisville, PA, 172.5 g solution used in reaction In) were mixed with ethanol (anhydrous, J.T. Baker, Phillipsburgh, NJ) and an aqueous hydrochloric acid solution (Aldrich, Milwaukee, WI) in a flask. Reactions Ia-Ir, Iu-Iy used 0.1 N HCl, reactions Is and It used 0.01 N HCl, reaction Iz used 0.1 M acetic acid (J.T. Baker). Hydroquinone (Aldrich, Milwaukee, WI) was also added to reaction Io (8.4 mg) and reaction Ip (17.6 mg) to prevent polymerization of the methacryloxypropyl groups. Product Iy was prepared following a literature protocol (as described in K. Unger, et. Al. Colloid & Polymer Science vol. 253 pp. 658-664 (1975)). The resulting solution was agitated and refluxed for 16 hours in an atmosphere of argon or nitrogen. Alcohol was removed from the flask by distillation at atmospheric pressure. Residual alcohol and volatile species were removed by heating at 95-120° C for 1-2 hours in a sweeping stream of argon or nitrogen. The resulting polyorganoalkoxy siloxanes were clear viscous liquids. The chemical formulas are listed in Table 1 for the organoalkoxysilanes used to make the product polyorganoalkoxysiloxanes (POS). Specific amounts are listed in Table 2 for the starting materials used to prepare products Ia-Ix. Structural analysis was performed using NMR spectroscopy.

EXAMPLE 2 Hybrid Inorganic/Organic material surrounding of Hybrid Particles.

To a suspension of 5 μm BEH porous hybrid particles (20 g, Waters Corporation, Milford, MA; 6.5%C; SSA = 190 m²/g; SPV = 0.80 cm³/g; APD = 155 A) of the formula (Oi 5SiCH₂CH₂SiOi ₅)(Si0₂)₄ (prepared following the method described in U.S. Patent 6,686,035) in ethanol (anhydrous, J.T.Baker, Phillipsburgh, NJ; 5 mL/g) was added POS Ia from Example 1. The solvent was slowly removed under reduced pressure in a rotary evaporator for 0.5-4 hours. The particles were isolated on 0.5 μm filtration paper and washed repeatedly using ethanol (anhydrous, J.T.Baker, Phillipsburgh, NJ). The material was then heated 50⁰C in a suspension with ethanol (3 mL/g, anhydrous, J.T.Baker, Phillipsburgh, NJ), deionized water (7 mL/g) and 30% ammonium hydroxide (20 g; J.T. Baker, Phillipsburgh, NJ) for 20 hours. The reaction was then cooled and the product was filtered and washed successively with water and methanol (J.T. Baker, Phillipsburgh, NJ). The product was then dried at 80 ⁰C under reduced pressure for 16 hours. Specific amounts of starting materials used to prepare these products are listed in Table 3. The %C values, specific surface areas (SSA), specific pore volumes (SPV) and average pore diameters (APD) of these materials are listed in Table 3.

Table 3

EXAMPLE 3 Hybrid Inorganic/Organic Material Surrounding of Hybrid Particles. To a suspension of 5 μm BEH porous hybrid particles (20 g, Waters Corporation, Milford,

MA; 6.5%C; SSA = 190 m²/g; SPV = 0.80 cm³/g; APD = 155 A) of the formula (Oi 5SiCH₂CH₂SiOi ₅)(Si0₂)₄ (prepared following the method described in U.S. Patent 6,686,035) in dry toluene (Fisher Scientific, Fairlawn, NJ; 5 mL/g) was added POS Ia from Example 1 and water. This reaction was heated at 8O⁰C for one hour and 110⁰C for 20 hours using a Dean-Stark trap to remove residual water. The reaction was cooled to room temperature and particles were isolated on 0.5 μm filtration paper and washed repeatedly using ethanol (anhydrous, J.T.Baker, Phillipsburgh, NJ). The material was then heated to 50⁰C in a suspension with ethanol (3 mL/g, anhydrous, J.T.Baker, Phillipsburgh, NJ), deionized water (7 mL/g) and 30% ammonium hydroxide (20 g; J.T.Baker, Phillipsburgh, NJ) for 4 hours. The reaction was then cooled and the product was filtered and washed successively with water and methanol (Fisher Scientific, Fairlawn, NJ). The product was then dried at 80 ⁰C under reduced pressure for 16 hours. Specific amounts of starting materials used to prepare these products are listed in Table 4. The %C values, specific surface areas (SSA), specific pore volumes (SPV), average pore diameters (APD), and changes in SPV (ΔSPV) are listed in Table 4.

The increase in carbon content (1.0-1.8%C) and reduction in SPV (0.10 cffiVg average change) were observed by this approach. SEM analysis indicated equivalent particle morphology and surface features of the starting particles. Particle size analysis (by Coulter Counter) indicated equivalent particle size and distribution of the starting particles. This suggests the decreased porosity of this Material Surrounding process is due to a filling of the porous particle framework, and is not due to the introduction of surface debris or a secondary nonporous particle distribution. The reduction in APD also indicates that this Material Surrounding process is filling the pore framework. The slight increase in SSA may indicate the surrounding material has a small degree of porosity.

Table 4

EXAMPLE 4 Hybrid Inorganic/Organic Material Surrounding of Hybrid Particles.

To a suspension of 3.5 μm BEH porous hybrid particles (Waters Corporation, Milford, MA; 6.5%C; SSA = 185 m²/g; SPV = 0.76 cm³/g; APD = 146A) of the formula (Oi 5SiCH₂CH₂SiOi ₅)(Si0₂)₄ (prepared following the method described in U.S. Patent 6,686,035) in dry toluene (Fisher Scientific, Fairlawn, NJ; 5 mL/g for 4a-4b; 10 mL/g for 4e-4i) was added POS Ia from Example 1 and water. This reaction was heated at 8O⁰C for one hour and 110⁰C for 20 hours. Reactions 4a and 4c did not employ the use of a Dean-Stark trap to remove residual water; while the other reactions used of a Dean-Stark trap. The reaction was cooled to room temperature and particles were isolated on 0.5 μm filtration paper and washed repeatedly using ethanol (anhydrous, J.T.Baker, Phillipsburgh, NJ). The material was then heated 50⁰C in a suspension with ethanol (3 mL/g, anhydrous, J.T.Baker, Phillipsburgh, NJ), deionized water (7 mL/g) and 30% ammonium hydroxide (20 g; J.T. Baker, Phillipsburgh, NJ) for 4 hours. The reaction was then cooled and the product was filtered and washed successively with water and methanol (Fisher Scientific, Fairlawn, NJ). The product was then dried at 80 ⁰C under reduced pressure for 16 hours. Specific amounts of starting materials used to prepare these products are listed in Table 5. The %C values, specific surface areas (SSA), specific pore volumes (SPV), average pore diameters (APD) and changes in SPV (ΔSSA) are listed in Table 5.

Increases in carbon content (1.0-2.6%C) and reductions in SPV (0.12-0.44 cffiVg) were achieved by this Material Surrounding approach. SEM analysis confirmed equivalent particle morphology and surface features of the starting particles. Particle size analysis (by Coulter Counter) indicated equivalent particle size and distribution of the starting particles. This suggests the decreased porosity of this Material Surrounding process is due to a filling of the porous particle framework, and is not due to the introduction of surface debris or a secondary nonporous particle distribution.

Table 5

EXAMPLE 5 Hydrothermal Processing of Hybrid Surrounded Hybrid Particles

As a means to modify the pore structure of surrounded hybrid particles, particles from Examples 3 and 4 were mixed with an aqueous solution of 0.3 M tris(hydroxymethyl)aminomethane (TRIS, Aldrich Chemical, Milwaukee, WI) at a slurry concentration of 5 mL/g. The pH of the resultant slurry was adjusted to 9.8 using acetic acid (J.T. Baker, Phillipsburgh, NJ). The slurry was then enclosed in a stainless steel autoclave and heated to 155 ⁰C for 20 hours. After cooling the autoclave to room temperature, the product was were isolated on 0.5 μm filtration paper and washed with water and methanol (Fisher Scientific, Suwanee, GA). The particles were then dried at 80 ⁰C under vacuum for 16 hours. Specific characterization data for these materials are listed in Table 6. Changes in product %C (Δ%C), SSA (ΔSSA) and APD (ΔAPD), relative to the precursor material from Examples 3 and 4, are listed in Table 6. This set of experiments showed that hydrothermal processing of surrounded hybrid particles could be used to modify the pore attributes of these materials. All products had noticeable reductions in SSA, increases in APD and no significant changes in SPV or particle morphology (as determined by SEM), when compared with the precursor materials from Examples 3 and 4. It was concluded that the use of hydrothermal treatment was successful in increasing the APD. The APD for these products was within a range that is comparable with commercially available HPLC packing materials. Reductions in %C for these products are due in part to a removal of surface alkoxides and the partial hydrolysis of the methacryloxypropyl group of the surrounding material. This hydrolysis results in the formation of a hydroxypropyl group (e.g., H0(CH₂)3Si0i ₅), as confirmed by NMR and FT-IR spectroscopy.

TABLE 6

EXAMPLE 6 Secondary Hybrid Inorganic/Organic Material Surrounding of Hybrid Particles.

To a suspension of porous hybrid particles from Example 5 in dry toluene (Fisher Scientific, Fairlawn, NJ; 10 mL/g) was added POS Ia from Example 1 and water. This reaction was heated at 80⁰C for one hour and 110⁰C for 20 hours using a Dean-Stark trap to remove residual water. The reaction was cooled to room temperature and particles were isolated on 0.5 μm filtration paper and washed repeatedly using ethanol (anhydrous, J.T.Baker, Phillipsburgh, NJ). The material was then heated to 50⁰C in a suspension with ethanol (3 mL/g, anhydrous, J.T.Baker, Phillipsburgh, NJ), deionized water (7 mL/g) and 30% ammonium hydroxide (20 g; J.T. Baker, Phillipsburgh, NJ) for 4 hours. The reaction was then cooled and the product was filtered and washed successively with water and methanol (Fisher Scientific, Fairlawn, NJ). The product was then dried at 80 ⁰C under reduced pressure for 16 hours. Specific amounts of starting materials used to prepare these products are listed in Table 7. The %C values, specific surface areas (SSA), specific pore volumes (SPV), average pore diameters (APD), and changes in SPV (ΔSPV) are listed in Table 7.

This set of experiments showed that repeated Material Surrounding can be used to further change the pore properties of these materials. Increases in carbon content (0.7 %C) and reduction in SPV (0.13 cm /g) were achieved with this Material Surrounding approach. Comparing these products with the unmodified BEH particle used in Example 3 and 4, we observe a larger increase in carbon content (1.00-1.36 %C) and a decrease in SPV (0.23-0.24 cm /g) have been achieved by this iterative process. SEM analysis confirmed equivalent particle morphology and surface features of the precursor materials.

Table 7

EXAMPLE 7 Hydrothermal Processing of Hybrid Inorganic/Organic Surrounded Hybrid Particles

Hybrid particles from Examples 6 were mixed with an aqueous solution of 0.3 M tris(hydroxymethyl)aminomethane (TRIS, Aldrich Chemical, Milwaukee, WI) at a slurry concentration of 5 mL/g. The pH of the resultant slurry was adjusted to 9.8 using acetic acid (J.T. Baker, Phillipsburgh, NJ). The slurry was then enclosed in a stainless steel autoclave and heated to 155 ⁰C for 20 hours. After cooling the autoclave to room temperature, the products were isolated on 0.5 μm filtration paper and washed with water and methanol (Fisher Scientific, Suwanee, GA). The particles were then dried at 80 ⁰C under vacuum for 16 hours. Specific characterization data for these materials are listed in Table 8. Changes in product %C (Δ%C), SSA (ΔSSA) and APD (ΔAPD), relative to the precursor material from Example 6, are listed in Table 8.

This set of experiments showed that hydrothermal processing of repeated surrounded hybrid particles could be used reduce the SSA, increase APD and have no significant changes in SPV or particle morphology (as determined by SEM), when compared with the precursor materials. Reductions in %C for these products are due in part to a removal of surface alkoxides of the precursor materials and the partial hydrolysis of the methacryloxypropyl group of the surrounding material. This hydrolysis results in the formation of a hydroxypropyl group {e.g., H0(CH₂)3Si0i ₅), as confirmed by NMR and FT-IR spectroscopy. TABLE 8

EXAMPLE 8

Hybrid Inorganic/Organic Material Surrounding of Hybrid Particles.

To a suspension of 3.0-3.5 μm BEH porous hybrid particles (20 g, Waters Corporation, Milford, MA; 6.5%C; SSA = 185-191 m²/g; SPV = 0.76-0.82 cm³/g; APD = 146-153 A) of the formula (Oi 5SiCH₂CH₂SiOi ₅)(Si0₂)₄ (prepared following the method described in U.S. Patent

6,686,035) in toluene (Fisher Scientific, Fairlawn, NJ; 10 mL/g) was added a POS from Example 1 (16.42 g) and deionized water (0.8 mL). Reactions 8u, 8v and 8ad used a 4.8 μm BEH porous particle. Reactions 8p and 8q used 8.2 mL of deionized water. Reactions 8s and 8t were performed at a two-fold increased scale, reactions 8w and 8x at ten- fold increased scale, and reaction 8y at 25- fold increased scale. Hydroquinone (30 ppm, Aldrich, Milwaukee, WI) was added to reactions 8n and 80 to prevent polymerization of the methacryloxypropyl group. Reactions were heated at 8O⁰C for one hour and 110⁰C for 20 hours using a Dean-Stark trap to remove residual water. The reaction was cooled to room temperature and particles were isolated on 0.5 μm filtration paper and washed repeatedly using ethanol (anhydrous, J.T.Baker, Phillipsburgh, NJ). The material was then heated 50⁰C in a suspension with ethanol (3 mL/g, anhydrous, J.T.Baker, Phillipsburgh, NJ), deionized water (7 mL/g) and 30% ammonium hydroxide (20 g; J.T. Baker, Phillipsburgh, NJ) for 4 hours. The reaction was then cooled and the product was filtered and washed successively with water and methanol (Fisher Scientific, Fairlawn, NJ). The product was then dried at 80 ⁰C under reduced pressure for 16 hours. The %C values, specific surface areas (SSA), specific pore volumes (SPV) and average pore diameters (APD) of these materials are listed in Table 9. Changes in product %C (Δ%C), and SPV (ΔSPV) are listed in Table 9.

This set of experiments showed that a variety of different POS can be used to create hybrid surrounded materials. This series of surrounded materials differ in hydrophobicity and surface activity. For example, the octadecyl groups of surrounded product 8d and partially fluorinated groups of surrounded product 8i may result in increased hydrophobicity over the unmodified BEH particles. The zirconium containing product 8m may display increased surface activity, which may be beneficial for some chromatographic separations. The hydrophobic and strong electron withdrawing nature of the perfluorophenyl containing surrounded product 8t may display both increased hydrophobicity and modified surface silanol activity. As shown with product 8b, the use of a POS with the formula (Oi 5SiCH₂CH₂SiOi ₅)(Si0₂)₄ resulted in hybrid surrounded particles that have the sample chemical composition as the unmodified particles, allowing for changes only in particle pore properties. Carbon content varied due to the composition of the surrounding material. For example, product 8b showed no change in carbon content. This was expected since the surrounding material and the base particle have the same chemical composition. The surrounding material of product 8t, which has a lower carbon content than the BEH material, resulted in a reduction in carbon content of the surrounded product. Products 8u-8y were repeat experiments aimed at determining the reproducibility of this process at increased reaction scale. These products have good reproducibility, having relative standard deviations less than 4.5% for %C, SSA, SPV, and APD data.

Reductions in SPV (-0.04 to -0.25 cm /g) were also achieved by this Material Surrounding approach. SEM analysis confirmed equivalent particle morphology and surface features of the starting particles. Particle size analysis (by Coulter Counter) indicated equivalent particle size and distribution to that of the starting particles.

Table 9

EXAMPLE 9 Hydrothermal Processing of Hybrid Coated Hybrid Particles

Hybrid particles from Examples 8 were mixed with an aqueous solution of 0.3 M tris(hydroxymethyl)aminomethane (TRIS, Aldrich Chemical, Milwaukee, WI) at a slurry concentration of 5 mL/g. The pH of the resultant slurry was adjusted to 9.8 using acetic acid (J.T. Baker, Phillipsburgh, NJ). The slurry was then enclosed in a stainless steel autoclave and heated to 155 ⁰C for 20 hours. After cooling the autoclave to room temperature, the product was isolated on 0.5 μm filtration paper and washed with water and methanol (Fisher Scientific, Suwanee, GA). The particles were then dried at 80 ⁰C under vacuum for 16 hours. Specific characterization data for these materials are listed in Table 10.

This set of experiments showed that hydrothermal processing of surrounded hybrid particles could be used reduce the SSA, increase APD and have no significant changes in SPV or particle morphology (as determined by SEM), when compared with the precursor materials. While most modifications in %C were small (<0.35 %C), larger reductions in %C for some of these products are due in part to a removal of surface alkoxides of the precursor materials and chemical modification of some of specific organo functional groups of the surrounding material. For example, the partial ester hydrolysis for products 9j, 9n, 9o, 9r and 9s results in the formation of a hydroxypropyl group {e.g., H0(CH₂)3Si0i ₅). The deprotection of the tert-butoxycarbonyl group for products 9k, 9p and 9q results in the formation of an aminopropyl gre.g.,e.g., NH₂(CH₂)3Si0i 5), as confirmed by NMR spectroscopy.

The modifications in pore structure obtained by hydrothermal treatment of an surrounded hybrid particle can be observed in the nitrogen desorption data (BJH dWdlog(D) pore volume data). As shown in Figure 1 for the Material Surrounding and hydrothermal treatment products 8b and 9b, respectively, noticeable changes in mean pore diameter are obtained by this process. The width of the pores size distribution decreased relative to the unmodified BEH hybrid particles as a result of this process. Repeat experiments, products 9u-9y, demonstrate good reproducibility with relative standard deviations for %C, SSA, SPV, and APD less than 4.5%.

EXAMPLE 10 Silica Based Material Surrounding of Hybrid Particles.

To a suspension of 3.5 μm BEH porous hybrid particles (Waters Corporation, Milford, MA; 6.5%C; SSA = 185 m²/g; SPV = 0.76 cm³/g; APD = 146A) of the formula (Oi 5SiCH₂CH₂SiOi ₅)(Si0₂)₄ (prepared following the method described in U.S. Patent 6,686,035) in dry toluene (Fisher Scientific, Fairlawn, NJ; 10 mL/g) was added POS Iy from Example 1 and deionized water. This reaction was heated at 8O⁰C for one hour and 110⁰C for 20 hours using a Dean-Stark trap to remove residual water. The reaction was cooled to room temperature and particles were isolated on 0.5 μm filtration paper and washed repeatedly using ethanol (anhydrous, J.T.Baker, Phillipsburgh, NJ). The material was then heated 50⁰C in a suspension with ethanol (3 mL/g, anhydrous, J.T.Baker, Phillipsburgh, NJ), deionized water (7 mL/g) and 30% ammonium hydroxide (20 g; J.T. Baker, Phillipsburgh, NJ) for 4 hours. The reaction was then cooled and the product was filtered and washed successively with water and methanol (Fisher Scientific, Fairlawn, NJ). The product was then dried at 80 ⁰C under reduced pressure for 16 hours. Specific amounts of starting materials used to prepare these products are listed in Table 11. The %C values, specific surface areas (SSA), specific pore volumes (SPV) and average pore diameters (APD) of these materials are listed in Table 11. Changes in product %C (Δ%C) and SPV (ΔSPV) are listed in Table 11.

This set of experiments showed that a tetraalkoxysilane-based POS can be used to create silica surrounded hybrid materials. This may allow for modification of particle surface properties (e.g., silanol activity and hydrophilicity). Carbon content, SSA, SPV and APD decreased as a result of silica Material Surrounding of these hybrid materials, which is due to the lack of carbon in the surrounding material (e.g., SiO₂). SEM analysis confirmed equivalent particle morphology and surface features of the starting particles. Particle size analysis (by Coulter Counter) indicated equivalent particle size and distribution of the starting particles.

EXAMPLE 11 Hydrothermal Processing of Silica Coated Hybrid Particles

Hybrid particles from Example 10 were mixed with an aqueous solution of 0.3 M tris(hydroxymethyl)aminomethane (TRIS, Aldrich Chemical, Milwaukee, WI) at a slurry concentration of 5 mL/g. The pH of the resultant slurry was adjusted to 9.8 using acetic acid (J.T. Baker, Phillipsburgh, NJ). The slurry was then enclosed in a stainless steel autoclave and heated to 155 ⁰C for 20 hours. After cooling the autoclave to room temperature, the product was isolated on 0.5 μm filtration paper and washed with water and methanol (Fisher Scientific, Suwanee, GA). The particles were then dried at 80 ⁰C under vacuum for 16 hours. Specific characterization data for these materials are listed in Table 12. This set of experiments showed that hydrothermal processing of silica surrounded hybrid particles could be used reduce the SSA, increase APD and have no significant changes in %C, SPV or particle morphology (as determined by SEM) when compared with the precursor materials.

TABLE 12

EXAMPLE 12

Addition of Nanoparticles to Polyorganosiloxanes

Diamond nanoparticles (Nanostructured & Amorphous Materials, Inc, Houston, TX, 4-25 nm) or silicon carbide nanoparticles (Sigma- Aldrich, Saint Louis, MO, <100 nm) were added to POS Ic in Example 1 to yield a 0.1-0.2 wt % dispersion. Dispersion was achieved using a rotor/stator mixer (Mega Sheer, Charles Ross & Son Co., Hauppauge, NY). Products were then centrifuged (Thermo EXD, 4 x 1 L bottle centrifuge, Milford, MA) to reduce agglomerates. Specific amounts are listed in Table 13 for the starting materials used to prepare these products.

TABLE 13

EXAMPLE 13

Nanoparticle Hybrid Composite Material Surrounding of Hybrid Particles.

To a suspension of 3.5 μm BEH porous hybrid particles (20 g, Waters Corporation, Milford,

MA; 6.5%C; SSA = 185 m²/g; SPV = 0.76 cm³/g; APD = 146A) of the formula

(Oi 5SiCH₂CH₂SiOi ₅)(Si0₂)₄ (prepared following the method described in U.S. Patent 6,686,035) in toluene (Fisher Scientific, Fairlawn, NJ; 10 mL/g) was added a POS from Example 12 (16.42 g) and deionized water (0.8 g). This reaction was heated at 8O⁰C for one hour and 110⁰C for 20 hours using a Dean-Stark trap to remove residual water. The reaction was cooled to room temperature and particles were isolated on 0.5 μm filtration paper and washed repeatedly using ethanol (anhydrous, J.T.Baker, Phillipsburgh, NJ). The material was then heated to 50⁰C in a suspension with ethanol (3 mL/g, anhydrous, J.T.Baker, Phillipsburgh, NJ), deionized water (7 mL/g) and 30% ammonium hydroxide (20 g; J.T. Baker, Phillipsburgh, NJ) for 4 hours. The reaction was then cooled and the product was filtered and washed successively with water and methanol (Fisher Scientific, Fairlawn, NJ). The product was then dried at 80 ⁰C under reduced pressure for 16 hours. The %C values, specific surface areas (SSA), specific pore volumes (SPV), average pore diameters (APD) and changes in SPV (ΔSPV) of these materials are listed in Table 14. This set of experiments showed that a nanoparticle containing POS can be used to create composite surrounding materials. This may allow for modification of particle properties (e.g., surface acidity, thermal and mechanical properties). A reduction in SPV (0.11 cm /g) was achieved by this composite Material Surrounding approach. SEM analysis confirmed equivalent particle morphology and surface features to that of the starting particles. Particle size analysis (by Coulter Counter) indicated equivalent particle size and distribution of the starting particles. This suggests the decreased porosity of this Material Surrounding process is due to a filling of the porous particle framework, and is not due to the introduction of surface debris or secondary nonporous particles.

Table 14

EXAMPLE 14

Hydrothermal Processing of Nanoparticle Hybrid Composite Surrounded Hybrid

Particles

Hybrid particles from Examples 13b were mixed with an aqueous solution of 0.3 M tris(hydroxymethyl)aminomethane (TRIS, Aldrich Chemical, Milwaukee, WI) at a slurry concentration of 5 mL/g. The pH of the resultant slurry was adjusted to 9.8 using acetic acid (J.T. Baker, Phillipsburgh, NJ). The slurry was then enclosed in a stainless steel autoclave and heated to 155 ⁰C for 20 hours. After cooling the autoclave to room temperature, the product was isolated on 0.5 μm filtration paper and washed with water and methanol (Fisher Scientific, Suwanee, GA). The particles were then dried at 80 ⁰C under vacuum for 16 hours. The resulting product 14a had 6.49 %C, a specific surface area (SSA) of 132 m²/g, a specific pore volume of 0.64 cffiVg, and an average pore diameter (APD) of 167 A. Hydrothermal processing of a composite surrounded hybrid material reduced SSA and increased APD without having a significant changes in SPV or particle morphology (as determined by SEM) when compared with the precursor materials.

EXAMPLE 15 Hybrid Inorganic/Organic Material Surrounding of Wider Pore Hybrid Particles.

To a suspension of wider pore BEH porous hybrid particles of the formula (Oi 5SiCH₂CH₂SiOi ₅)(Si0₂)₄ (prepared following the method described in U.S. Patent 6,686,035) denoted Type A (3.5 μm; 6.3%C; SSA = 38 m²/g; SPV = 0.67 cm³/g; APD = 600 A; MPV = 0.67 cm³/g; MPD = 513 A), Type B (3.5 μm; 6.6 %C; SSA = 83 m²/g; SPV = 0.65 cm³/g; APD = 287 A; MPV = 0.61 cm³/g; MPD = 243 A), or Type C (5 μm; 6.44 %C; SSA = 95-100 m²/g; SPV = 0.81- 0.83 cm³/g; APD = 289-324 A; MPV = 0.77-0.83 cm³/g; MPD = 252-265 A) in toluene (Fisher Scientific, Fairlawn, NJ; 10 mL/g) was added a POS from Example 1 and deionized water.

Reactions were heated at 8O⁰C for one hour and 110 ⁰C for 20 hours. For reactions 15a and 15b a Dean-Stark trap was used to remove residual water. The reaction was cooled to room temperature and particles were isolated on 0.5 μm filtration paper and washed repeatedly using ethanol (anhydrous, J.T.Baker, Phillipsburgh, NJ). The material was then heated 50⁰C in a suspension with ethanol (3 mL/g, anhydrous, J.T.Baker, Phillipsburgh, NJ), deionized water (7 mL/g) and 30% ammonium hydroxide (20 g; J.T. Baker, Phillipsburgh, NJ) for 4 hours. The reaction was then cooled and the product was filtered and washed successively with water and methanol (Fisher Scientific, Fairlawn, NJ). The product was then dried at 80 ⁰C under reduced pressure for 16 hours. The %C values and specific surface areas (SSA) of these materials are listed in Table 15. The median mesopore diameter (MPD) and mesopore pore volume (MPV), measured by Mercury Porosimetry are listed in Table 15. Changes in product SPV (ΔSPV) and MPV (ΔMPV), relative to the unmodified hybrid particles, are listed in Table 15.

This set of experiments showed that a hybrid POS can be used to create surrounded wider pore diameter hybrid materials. This may allow for modification of particle surface properties, and mechanical properties. A reduction in pore volume may allow for improvements in mechanical strength of the porous network. Reduction in MPV (0.06 - 0.16 cm /g) were achieved by this composite Material Surrounding approach. SEM analysis confirmed equivalent particle morphology and surface features of the starting particles. Particle size analysis (by Coulter Counter) indicated equivalent particle size and distribution to that of the starting particles.

EXAMPLE 16

Hydrothermal Processing of Hybrid Surrounding material with Wider Pore Particles

Hybrid particles from Examples 15 were mixed with an aqueous solution of 0.3 M tris(hydroxymethyl)aminomethane (TRIS, Aldrich Chemical, Milwaukee, WI) at a slurry concentration of 5 mL/g. The pH of the resultant slurry was adjusted to 9.8 using acetic acid (J.T. Baker, Phillipsburgh, NJ). The slurry was then enclosed in a stainless steel autoclave and heated to 155 ⁰C for 20 hours. After cooling the autoclave to room temperature, the product was isolated on 0.5 μm filtration paper and washed with water and methanol (Fisher Scientific, Suwanee, GA). The particles were then dried at 80 ⁰C under vacuum for 16 hours. Specific characterization data for these materials are listed in Table 16. Hydrothermal processing of a surrounding material with wider pore hybrid material reduced SSA and increased MPD without a significant changes in %C or particle morphology (as determined by SEM) when compared with the precursor materials. A high resolution SEM of product 16a indicates that a highly porous pore network is maintained by this process.

TABLE 16

EXAMPLE 17

Acid Treatment of Hybrid Particles with Surrounding Material

Porous particles prepared according to Examples 5, 9 and 11 were dispersed in a 1 molar hydrochloric acid solution (Aldrich, Milwaukee, WI) for 20 h at 98°C. The particles were isolated on 0.5 μm filtration paper and washed with water to a neutral pH, followed by acetone (HPLC grade, Fisher Scientific, Fairlawn, N. J.). The particles were dried at 80⁰C under vacuum for 16 h. Specific characterization data for these materials are listed in Table 17.

While no significant changes in SSA, SPV or APD occurred with respect to the precursor materials, there are noticeable reductions in SSA (reduced 13-63 m²/g) and SPV (reduced 0.05-0.23 cm3/g) with respect to the unmodified BEH hybrid particles.

With the exception of product 17k and 171, no significant changes in %C occurred with respect to the precursor materials. The loss in %C for these two products (reduced 0.41-0.75%C) may have resulted in deprotection of remaining fert-butoxycarbonyl groups, resulting in the formation of an aminopropyl group (e.g., NH₂(CH₂)3Si0i ₅). Changes in %C, with respect to the unmodified BEH hybrid increased or decreased due to the chemical formula of the surrounding material. The micropore surface area (MSA) for these materials are all within the requirement for chromatographic material having chromatographically enhanced pore geometry. Repeat experiments, products 17t- 17x, demonstrate good reproducibility with relative standard deviations for %C, SSA, SPV, and APD less than 5%.

TABLE 17

EXAMPLE 18 Reaction of Hybrid Particles with a Surrounding Material with Isocyanates

Hydroxypropyl containing Hybrid particles with a surrounding material from Example 17 were modified with octadecyl isocyanate (ODIC, Aldrich Chemical), dodecyl isocyanate (DIC, Aldrich Chemical), pentafluorophenyl isocyanate (PFPIC, Aldrich Chemical), 1 -adamantly isocyanate (AIC, Aldrich Chemical), 4-cyanophenyl isocyanate (4CPIC, Aldrich Chemical), 3- cyanophenyl isocyanate (3CPIC, Aldrich Chemical), 4-biphenylyl isocyanate (BPIC, Aldrich Chemical), 2,2-Diphenylethyl isocyanate (DPEIC, Aldrich Chemical), 3,5-dimethoxyphenyl isocyanate (DMPIC, Aldrich Chemical), 4-iodophenyl isocyanate (IPIC, Aldrich Chemical), 4- (chloromethyl)phenyl isocyanate (CMPIC, Aldrich Chemical), methyl (5)-(-)-2-isocyanato-3- phenylpropionate (MIP, Aldrich, Milwaukee, WI), phenyl isocyanate (PIC, Aldrich Chemical), benzyl isocyanate (BIC, Aldrich Chemical), or phenethyl isocyanate (PEIC, Aldrich Chemical) in dry toluene (5 mL/g, J.T.Baker) under an argon blanket. The suspension was heated to reflux (110⁰C) for 16 h and then cooled to <30°C. Product 18g was prepared in refluxing xylenes (30 mL/g, J.T. Baker). The particles were transferred to a filter apparatus and washed exhaustively with toluene and acetone. The material was then heated for an hour at 50⁰C in a 1 : 1 v/v mixture of acetone and 1 % trifluoroacetic acid (Aldrich, Milwaukee, WI ) solution (10 mL/g particles, Hydrolysis type A), or in a 60:40 v/v mixture of acetone and 100 mM ammonium bicarbonate (pH 8, Aldrich, Milwaukee, WI) for 20 hours (Hydrolysis type B), or in a 60:40 v/v mixture of acetone and 100 mM ammonium bicarbonate (pH 10, Aldrich, Milwaukee, WI) for 20 hours (Hydrolysis type C). Product 18r was heated for 1 hour. The reaction was then cooled and the product was filtered and washed successively with acetone and toluene (heated at 70⁰C). The product was then dried at 70 ⁰C under reduced pressure for 16 hours. Reaction data is listed in Table 18. The surface coverage of carbamate groups was determined by the difference in particle %C before and after the surface modification as measured by elemental analysis.

EXAMPLE 19

Secondary Surface Modification of Hybrid Particles with a surrounding material with

Isocyanates

The material of Example 18 were further modified with octadecyl isocyanate (ODIC, Aldrich

Chemical), ?-butyl isocyanate (TBIC, Aldrich Chemical), or n-butyl isocyanate (NBIC, Aldrich Chemical) in dry toluene (5 mL/g, J.T.Baker) under similar reaction conditions as Example 18. Reaction data is listed in Table 19. The additional surface coverage of carbamate groups was determined by the difference in particle %C before and after the surface modification as measured by elemental analysis.

TABLE 19

EXAMPLE 20 Modification of Hybrid Particles with a Surrounding Material with Chlorosilanes

The materials of Example 18 and 19 were further modified with either trimethylchlorosilane (TMCS, Gelest Inc., Morrisville, PA), triethylchlorosilane (TECS, Gelest Inc., Morrisville, PA), triisopropylchlorosilane (TIPCS, Gelest Inc., Morrisville, PA), thexyldimethylchlorosilane (TDMCS, Gelest Inc., Morrisville, PA), tert-butyldimethylchlorosilane (TBDMCS, Gelest Inc., Morrisville, PA), l-(tert-Butyldimethylsilyl)imidazole (TBDMSI, TCI America), or tert- butyldiphenylchlorosilane (TBDPCS, Gelest Inc., Morrisville, PA) using imidazole (Aldrich, Milwaukee, WI) in refluxing toluene (5 mL/g) for 4 hours. The reaction was then cooled and the product was filtered and washed successively with water, toluene, 1 : 1 v/v acetone/water and acetone (all solvents from J.T. Baker) and then dried at 80 ⁰C under reduced pressure for 16 hours. Product 2Of was performed for 20 hours. Products 2Of, 2Oi, 2Oj, 20k, and 201 underwent a subsequent reaction with TMCS under similar reaction conditions. Reaction data are listed in Table 20.

TABLE 20

EXAMPLE 21

Initial Surface Modification of Hybrid Particles with a Surrounding Material with Chlorosilanes

Samples from Example 17 were modified with octadecyltrichlorosilane (OTCS, Aldrich,

Milwaukee, WI) or octadecyldimethylchlorosilane (ODMCS, Gelest Inc., Morrisville, PA) using imidazole (Aldrich, Milwaukee, WI) in refluxing toluene (HPLC grade, Fisher Scientific, Fairlawn, NJ) for 4 hours. The reaction was then cooled and the product was filtered and washed successively with toluene, 1 : 1 v/v acetone/water and acetone (all solvents from J.T. Baker). For product 21a, the material was then refluxed in an acetone / aqueous 0.12 M ammonium acetate solution (Sigma

Chemical Co., St. Louis, MO) for 2 hours. The reaction was then cooled and the product was filtered and washed successively with toluene, 1 : 1 v/v acetone/water and acetone (all solvents from J.T. Baker). The product was then dried at 80 ⁰C under reduced pressure for 16 hours. Reaction data is listed in Table 21. The surface coverage of Cig-groups was determined by the difference in particle %C before and after the surface modification as measured by elemental analysis. TABLE 21

EXAMPLE 22

Chlorosilanes

The surface of the Cig-bonded hybrid material of Example 21a (14 g) was further modified with triethylchlorosilane (2.76 g, TECS, Gelest Inc., Morrisville, PA) using imidazole (1.50 g,

Aldrich, Milwaukee, WI) in refluxing toluene (75 mL) for 4 hours. The reaction was then cooled and the product was filtered and washed successively with water, toluene, 1 : 1 v/v acetone/water and acetone (all solvents from J.T. Baker) and then dried at 80 ⁰C under reduced pressure for 16 hours. The materials were then mixed with hexamethyldisilazane (HMDS, Gelest Inc., Morrisville, PA) yielding a slurry (concentration 1.1 g HMDS per 1.0 g particles). The resultant slurry was then enclosed in a stainless steel autoclave and heated at 200 ⁰C for 18 hours. After the autoclave cooled to room temperature the product was isolated on filtration paper and washed successively with water, toluene, 1 :1 v/v acetone/water and acetone (all solvents from J.T. Baker) and then dried at 80 ⁰C under reduced pressure for 16 hours. The product (22a) had 14.04 %C.

EXAMPLE 23

Chlorosilanes

The surface of the hybrid particle with a surrounding material from Examples 17 and 21 were modified with trimethylchlorosilane (TMCS, Gelest Inc., Morrisville, PA) using imidazole (Aldrich, Milwaukee, WI) in refluxing toluene for 4 hours. The reaction was then cooled and the product was filtered and washed successively with water, toluene, 1 : 1 v/v acetone/water and acetone (all solvents from J.T. Baker) and then dried at 80 ⁰C under reduced pressure for 16 hours. Reaction data are listed in Table 22. TABLE 22

EXAMPLE 24

Sub-1 μm Particle Containing Hybrid Inorganic/Organic Material Surrounding of Hybrid

Particles.

To a suspension of 3.5 μm BEH porous hybrid particles (20 g, Waters Corporation, Milford, MA; 6.5%C; SSA = 188 m²/g; SPV = 0.78 cm³/g; APD = 150 A) of the formula (Oi 5SiCH₂CH₂SiOi ₅)(Si0₂)₄ (prepared following the method described in U.S. Patent 6,686,035) in toluene (Fisher Scientific, Fairlawn, NJ; 10 mL/g) was added a dispersion of < 0.5 μm BEH porous hybrid particles within POS Ic from Example 1, and water (0.82 mL). The dispersion of <0.5 μm BEH porous hybrid particles (particle size determined by SEM) within POS Ic was achieved for examples 24a and 24b by stirring overnight. The dispersion for example 24c required initial dilution in ethanol, followed by vacuum distillation of ethanol. This Material Surrounding reaction was heated at 8O⁰C for one hour and 110⁰C for 20 hours. The reaction was cooled to room temperature and particles were isolated on 0.5 μm filtration paper and washed repeatedly using ethanol

(anhydrous, J.T.Baker, Phillipsburgh, NJ). The material was then heated to 50⁰C in a suspension with ethanol (3 mL/g, anhydrous, J.T.Baker, Phillipsburgh, NJ), deionized water (7 mL/g) and 30% ammonium hydroxide (20 g; J.T. Baker, Phillipsburgh, NJ) for 4 hours. The reaction was then cooled and the product was filtered and washed successively with water and methanol (Fisher Scientific, Fairlawn, NJ). The product was then dried at 80 ⁰C under reduced pressure for 16 hours. Specific amounts of starting materials used to prepare these products are listed in Table 23. The %C values, specific surface areas (SSA), specific pore volumes (SPV), average pore diameters (APD) and change in SPV (ΔSPV) of these materials are listed in Table 23. SEM analysis indicated the presence of surface < 0.5 μm particulates on the 3.5 μm particles.

Table 23

EXAMPLE 25 Acetoxy propyl Bondings on Hybrid Particles.

To a suspension of BEH porous hybrid particles (Type A, Waters Corporation, Milford,

MA; 6.5%C; SSA = 190 m²/g; SPV = 0.80 cm³/g; APD = 155 A) or 3 μm wider pore BEH porous particles (Type B, Waters Corporation, Milford, MA; 6.5%C; SSA = 88 m²/g; SPV = 0.68 cm³/g; APD = 285 A) of the formula (Oi 5SiCH₂CH₂SiOi ₅)(Si0₂)₄ (prepared following the method described in U.S. Patent 6,686,035) in toluene (HPLC grade, Fisher Scientific, Fairlawn, NJ) were modified with 3-acetoxypropyltrichlorosilane (ATPTCS, Silar Laboratories, Scotia, NY) and imidazole (Aldrich, Milwaukee, WI) and deionized water in refluxing toluene (HPLC grade, Fisher Scientific, Fairlawn, NJ) for 20 hours. Reaction 25a used 5 μm particles, and Reactions 25g and 25h used 3.5 μm particles. The reaction was then cooled and the material was filtered and washed successively with toluene, 1 :1 v/v acetone/water and acetone (all solvents from Fisher Scientific, Fairlawn, NJ). The material was then refluxed in an acetone / aqueous 0.12 M ammonium acetate solution (Sigma Chemical Co., St. Louis, MO) for 2 hours. The reaction was then cooled and the product was filtered and washed successively with toluene, 1 : 1 v/v acetone/water and acetone (all solvents from J.T. Baker). The product was then dried at 80 ⁰C under reduced pressure for 16 hours. The material was then dispersed in a 1 molar hydrochloric acid solution (Aldrich, Milwaukee, WI) for 20 h at 98- 100⁰C to yield hydroxypropyl groups {e.g., H0(CH₂)₃Si0i ₅), as confirmed by NMR spectroscopy. The particles were isolated on 0.5 μm filtration paper and washed with water to a neutral pH, followed by acetone (HPLC grade, Fisher Scientific, Fairlawn, NJ). The particles were dried at 8O⁰C under vacuum for 16 h. Reaction data is listed in Table 24. Product 25h was also hydrothermally treated following the procedure in Experiment 9, and was acid treated following the procedure in

Experiment 17. The surface coverage of hydroxypropyl groups was determined by the difference in particle %C before and after the surface modification as measured by elemental analysis.

TABLE 24

EXAMPLE 26 Reaction of Bonded Hybrid Particles with Isocyanates

Particles from Example 25a (20 g)were modified with octadecyl isocyanate (9.99 g, Aldrich

Chemical) in dry toluene (100 mL, Fisher Scientific, Fairlawn, NJ) under an argon blanket. The suspension was heated to reflux (110⁰C) for 16 h and then cooled to <30°C. The particles were transferred to a filter apparatus and washed exhaustively with toluene and acetone. The material was then heated for an hour at 50⁰C in a 1:1 v/v mixture of acetone and 1% trifluoroacetic acid (Aldrich, Milwaukee, WI) solution (100 mL). The reaction was then cooled and the product was filtered and washed successively with acetone and toluene (heated at 70⁰C). The material was then dried at 70 ⁰C under reduced pressure for 16 hours. The carbon content of this material was 13.32%C, and the surface coverage of carbamate groups was 1.73 μmol/m , determined by the difference in %C before and after the surface modification as measured by elemental analysis. The surface of these particles were modified with trimethylchlorosilane (TMCS, Gelest Inc., Morrisville, PA) using imidazole (Aldrich, Milwaukee, WI) in refluxing toluene for 4 hours. The reaction was then cooled and the product was filtered and washed successively with water, toluene, 1 : 1 v/v acetone/water and acetone (all solvents from J.T. Baker) and then dried at 80 ⁰C under reduced pressure for 16 hours. The final carbon content of the product (26a) was 14.24 %C.

EXAMPLE 27

Chromatographic Evaluation of Porous Hybrid Particles with a surrounding material

Samples of porous particles from Example 18, 20, 23 and 26 were used for the separation of a mixture of neutral, polar and basic compounds listed in Table 25. The 2.1x100 mm chromatographic columns were packed using a slurry packing technique. The chromatographic system consisted of an ACQUITY UPLC^® System and an ACQUITY UPLC^® Tunable UV detector. Empower 2 Chromatography Data Software (Build 2154) was used for data collection and analysis. Mobile phase conditions were: 20 mM K₂HPO₄ZKH₂PO₄, pH 7.00±0.02 / methanol (36/65 v/v); flow rate: 0.25 mL/min; temperature: 23.4°C; detection: 254 nm. It can be seen that these porous hybrid particles with a surrounding material provide sufficient retention and resolution in the separation of neutral, polar, and basic compounds. Relative retention is the retention time of the analyte divided by the retention time of acenaphthene. Therefore values less than one, indicate less retention than acenaphthene, and values greater than one, indicate more retention than acenaphthene. (Relative retention is a well known parameter in the field of HPLC.)

TABLE 25

EXAMPLE 28

Peak Shape Evaluation of Porous Hybrid Particles with a Surrounding Material

Samples of porous particles from Example 18, 20, 23 and 26 were evaluated for USP peak tailing factors using the mobile phase and test conditions of Example 25. The results are shown in Table 26. Peak tailing factors is a well known parameter in the field of HPLC (a lower value corresponds to reduced tailing). It is evident that the peak tailing factors these porous hybrid particles having a surrounding material have comparable basic compound tailing factors of commercially available Cig-columns.

TABLE 26

EXAMPLE 29

Chromatographic Evaluation of Porous Hybrid Particles having a Surrounding Material Samples of porous particles from Example 9 and 17 were used for the separation of a mixture of neutral, polar and basic compounds listed in Table 27. The 2.1x100 mm chromatographic columns were packed using a slurry packing technique. The chromatographic system consisted of an ACQUITY UPLC^® System and an ACQUITY UPLC^® Tunable UV detector. Empower 2 Chromatography Data Software (Build 2154) was used for data collection and analysis. Mobile phase conditions were: 100 mM ammonium formate, pH .3.00±0.02 / acetonitrile (10/90 v/v); flow rate: 0.5 mL/min; temperature: 23.4°C; detection: 254 nm.

It can be seen that these porous hybrid particles provide sufficient retention and resolution in the separation of polar compound under Hydrophilic Interaction Chromatography (HILIC) test conditions. Relative retention is the retention time of the analyte divided by the retention time of thymine. Therefore, values less than one, indicate less retention than thymine, and values greater than one, indicate more retention than acenaphthene. (Relative retention is a well known parameter in the field of HPLC) t-Boc protected aminopropyl hybrid particles having a surrounding material, 9q, showed low retention times for all analytes under these test conditions. This is expected due to the increased hydrophobicity of the t-Boc group. The deprotected aminopropyl surrounding hybrid particles, 171, resulted in a significant increase in retentivity.

TABLE 27

EXAMPLE 30

Peak Shape Evaluation of Porous Hybrid Particles with a Surrounding Material

Samples of porous particles from Example 9 and 17 were evaluated for USP peak tailing factors using the mobile phase and test conditions of Example 27. The results are shown in Table 28. Peak tailing factor is a well known parameter in the field of HPLC (a lower value corresponds to reduced tailing). It is evident that the porous hybrid particles having a surrounding material have comparable basic compound tailing factors of commercially available Hydrophilic Interaction Chromatography (HILIC) columns.

TABLE 28

EXAMPLE 31

Low pH Chromatographic Stability Test

Surface derivatized hybrid porous particles from Examples 18, 20 and 26 as well as selected commercial columns (Cig Type) based on silica, which have similar alkyl silyl groups, were evaluated for stability in acidic mobile phases using the following procedure. Columns were prepared by slurry packing the materials into 2.1x50mm steel columns and were tested on the following instrument configuration: Waters ACQUITY UPLC™ system was used for solvent delivery, sample injection (1 μL on a 5 μL loop using partial loop injection), UV detection (50OnL flow cell, Absorbance: 254 nm) and column heating at 60⁰C. Analysis conditions were as follows: 1) the retention time was measured for a test analyte, methyl paraben (100 μg/mL sample); 2) mobile phase conditions were 0.5% aqueous TFA at a flow of 1.4 mL/min and a column temperature of 60⁰C; and 3) 20 minute run times for 61 repeated injections under the same isocratic test conditions were used. The percent changes in the retention time are reported for final injections for methyl paraben, with respect to the retention obtained on the third injection. The results are shown in Table 29.

It is evident that the lifetimes of most of the columns containing hybrid particles having a surrounding material had similar chemical stability with respect to commercial columns containing silica-based materials (lower percent loss in original retention for each injection corresponds to improved chemical stability).

TABLE 29

EXAMPLE 32 Hydrolytic stability test The hydrolytic stability of the columns packed with porous hybrid particles from Example 17, 18, 20, 22, and 26 as well as some comparison columns were evaluated using the following procedure. Columns (3 x 30 mm) were equilibrated in 1:1 acetonitrile/water (210 minutes) before initial chromatographic performance was tested using uracil and decanophenone (1 :1 acetonitrile/water; 0.43 mL/min). The columns were then heated at 50⁰C and were challenged with a solution of 0.02 N NaOH in water (pH 12.3, 0.85 mL/min for 60 min) before flushing with 10:90 methanol/water followed by methanol. Chromatographic performance was reassessed at regular intervals by equilibrating the columns with acetonitrile (50 minutes), followed by testing using uracil and decanophenone (1:1 acetonitrile/water or 0.1% formic acid in 30:70 methanol/water, 0.43 mL/min). This process was repeated and the performance of the column was monitored until column failure. Column failure is defined as the time when the plate number drops to 50% of the initial value or when the test system shut down due to high column pressure. The results of these tests, including final reported loss in original column efficiency are shown in Table 30. Comparison Column A was commercially available 5 μm porous hybrid particles of the formula (Oi 5SiCH₂CH₂SiOi ₅)(Si0₂)₄, that was surface modified with C_IgH₃₇SiCIs followed by endcapping. Comparison Column B (repeated on three separate columns) was 3.5 μm porous hybrid particles of the formula (Oi 5SiCH₂CH₂SiOi ₅)(Si0₂)₄, that was surface modified with CH₃(CH₂)iiNHCO₂(CH₂)3Si(CH₃)₂Cl followed by endcapping. Comparison Column C was a commercially available 3 μm silica-core particle that was surface modified with an organofunctional silane followed by Cig surface modification. Comparison Column D was commercially available 5 μm porous hybrid particles of the formula (CH₃SiOi ₅)(Si0₂)₂, that was surface modified with C_IgH₃₇SiCl₃ followed by endcapping. Comparison Column E was commercially available 5 μm porous silica particles that was surface modified with CigH₃₇Si(CH₃)₂Cl followed by endcapping.

Comparison Column A and B (which is based on a hybrid formula that is substantially enriched in silica content) failed under these test conditions between 22-52 hours exposure to 0.02 N NaOH. Hybrid Column E failed within 3 hours exposure to 0.02 N NaOH. Comparison Column C and E (which are based on a silica base particle) failed under these test conditions at 3-5 hours exposure to 0.02 N NaOH. It is well known in the field of HPLC that column failure resulting in high column pressure when silica based columns are exposed to alkaline solutions can result from the dissolution of the silica particle resulting in the collapse of the column bed. For Comparison Column B this packed-bed collapse was confirmed by column dissection and the measurement of a 10 mm void at the inlet of the column. It can be concluded that the durability of the porous hybrid packing materials from Example 17, 20 and 22 are improved over the both Comparison Columns C, D, and E, and are comparable to Comparison Columns A and B under these test conditions.

TABLE 30

EXAMPLE 33

Selectivity Comparison of Surrounding Porous Hybrid Particles having a Surrounding Material with a Commercial C18 column Chromatographic selectivity differences for select products from Example 18 and 20 were evaluated under pH 7 and pH 3 test conditions (2.1x100 mm columns). System conditions were the same as detailed in Experiment 27. Mobile phase conditions were: 20 mM K₂HPO₄/KH₂PO₄, pH 7.00±0.02 / methanol (36/65 v/v) or 15.4 mM ammonium formate, pH 3.0 / acetonitrile (65/35 v/v); flow rate: 0.25 mL/min, temperature: 23°C; detection: 254 nm. pH 7 test molecules included uracil, propranolol, butylparaben, naphthalene, dipropylphthalate, acenaphthene, and amitriptyline. pH 3 test molecules included uracil, pyrenesulfonic acid, desipramine, amitriptyline, butylparaben, and toluene. The correlation coefficient (R²) for retention times were made with a commercially available Cl 8 column (XBridge C 18, Waters Corporation) under both pH 7 and pH 3 test conditions. The selectivity value was calculated by 100(1 - R²)⁰⁵ as shown in Table 31. A lower R² and higher Selectivity Value indicate a greater selectivity difference under these test conditions. It can be concluded that surface modification of hybrid particles under conditions used in Examples 18 and 20 provide a different chromatographic selectivity under these test conditions.

TABLE 1

EXAMPLE 34

Reaction of Chloromethylphenyl containing Porous Hybrid Particles with a Surrounding

Material with Piperazine

Chloromethylphenyl containing particles 18w from Experiment 18 were further modified with piperazine (Acros, Geel Belgium) in refluxing toluene (110⁰C, HPLC grade, Fisher Scientific, Fairlawn, NJ) for 20 hours. The reaction was then cooled and the material was filtered and washed successively with toluene, 1 : 1 v/v acetone/water and acetone (all solvents from J.T. Baker). The product was then dried at 80 ⁰C under reduced pressure for 16 hours. Reaction data is listed in Table 32. The surface coverage of piperazyl groups (e.g.,

Oi 5Si(CH₂)3OC(O)NHC₆H₄CH₂N(CH₂CH₂)₂NH) was determined by the difference in particle %C before and after the surface modification as measured by elemental analysis.

TABLE 32

EXAMPLE 35 Reaction ofPropanol containing Porous Hybrid Particles with a Surrounding Material using

1,1 '-carbonyldiimidazole

Propanol containing hybrid particles from Example 17 were modified with 1,1'- carbonyldiimidazole (CDI, Fluka, Buchs, Switzerland) in toluene (ToI, 5 mL/g, Fisher Scientific, Fairlawn, NJ) for 2 hours at room temperature, or in dimethylformamide (DMF, 5 mL/g, Aldrich) for 20 hours at room temperature. Reactions performed in toluene were transferred to a filter apparatus and washed exhaustively with toluene, before redispersing in toluene. Octadecylamine (ODA, Fluka), octylamine (OA, Aldrich), 4-aminophenol (AP, Aldrich), tris(hydroxymethyl)methylamine (TRIS, Aldrich, dissolved in DMF at 60⁰C), or pentafluorophenylamine (PFPA, Aldrich) was then added and the reaction was stirred for an additional 20 hours. Specific reaction conditions are provided in Table 33. The product was filtered and washed successively with acetone, toluene, water and/or DMF. The material was then dried at 70 ⁰C under reduced pressure for 16 hours. Product 35b and 35c were further heated for an hour at 50 °C in a 1 : 1 v/v mixture of acetone and 1 % trifluoroacetic acid (Aldrich, Milwaukee, WI ) solution (10 mL/g particles), and products 35f and 35g were further heated for 20 hours at 50 °C in a 60:40 v/v misture of acetone and 100 mM ammonium bicarbonate (pH 8, Aldrich, Milwaukee, WI). The reaction was then cooled and the product was filtered and washed successively with acetone and toluene (heated at 70⁰C). The product was then dried at 70 ⁰C under reduced pressure for 16 hours. Product data is listed in Table 33. Product 35e was obtained by repeating this process on product 35d. The surface coverage of carbamate groups was determined by the difference in particle %C before and after the surface modification as measured by elemental analysis TABLE 33

EXAMPLE 36 Hybrid Monolith with a Surrounding Material.

Hybrid inorganic/organic monoliths of the formula (Oi 5SiCH₂CH₂SiOi ₅)(Si0₂)₄ (which is prepared following the method described in US patent No. 7,250,214) are soaked in toluene (J.T. Baker, 20 mL/g) and refluxed for 3.5 hours under an argon atmosphere to deoxygenate and to remove adsorbed water via azeotropic distillation. After cooling to room temperature under, POS Ic from Example 1 (0.8-1.6 g/g) and deionized water (0.04-0.2 mL/g) is added. The reaction is heated at 8O⁰C for one hour and 110⁰C for 20 hours using a Dean-Stark trap to remove residual water. Alternatively the Dean-Stark trap is not employed to remove residual water from the reaction. The reaction is cooled to room temperature and monoliths are washed repeatedly using ethanol (anhydrous, J.T.Baker, Phillipsburgh, NJ).

The material is then heated at 50⁰C in a suspension with ethanol (3 mL/g, anhydrous, J.T.Baker, Phillipsburgh, NJ), deionized water (7 mL/g) and 30% ammonium hydroxide (20 g; J.T. Baker, Phillipsburgh, NJ) for 4 hours. The reaction is then cooled and the product is washed successively with water and methanol (Fisher Scientific, Fairlawn, NJ). The product is dried at 80 ° C under reduced pressure for 16 hours.

This Material Surrounding of hybrid inorganic/organic monoliths can be performed using a variety of hybrid inorganic/organic POS' from Example 1 (Ia-Ix), nanoparticle containing POS from Example 12, or sub-1 μm particle containing POS as detailed in Example 24. Silica hybrid monoliths with a surrounding material can also be prepared using POS Iy from Example 1. This Material Surrounding of hybrid inorganic/organic monoliths can be performed in a reactor, or within a chromatographic device (e.g., microbore tubes, extraction cartridges, capillary tubes) under a pressurized flow of solvent and reagents, or it can be performed under stop-flow conditions. This Material Surrounding can be performed using a variety of hybrid monoliths, including other hybrid monoliths detailed in US patent No. 7,250,214, hybrid monoliths prepared from the condensation of one or more monomers that contain 0-99 mole percent silica (e.g., SiC^), hybrid monoliths prepared from coalesced porous inorganic/organic particles (also detailed in US patent No. 7,250,214), hybrid monoliths that have a chromatographically-enhancing pore geometry, hybrid monoliths that do not have a chromatographically-enhancing pore geometry, hybrid monoliths that have ordered pore structure, hybrid monoliths that have non-periodic pore structure, hybrid monoliths that have noncrystalline or amorphous molecular ordering, hybrid monoliths that have crystalline domains or regions, hybrid monoliths with a variety of different macropore and mesopore properties, and hybrid monoliths in a variety of different aspect ratios.

EXAMPLE 37 Formation of Hybrid Monoliths with Porous Hybrid Particles having a Surrounding Material. Hybrid inorganic/organic particles having a surrounding material from Examples 8-11 and

Examples 13-24 are mixed with 5 μm Symmetry silica (Waters Corporation, 0-50 % weight) to yield 6 g total mass. The mixture is dispersed in an appropriate solvent (e.g., isopropanol / tetrahydrofuran mixtures) for 5 minutes, before slurry packing into 2.1x50 mm HPLC columns using a downward slurry technique with a high-pressure liquid packing pump. After completion of column packing, the pressure is released and the end fitted column is transferred to chromatographic pump station (Waters 590 HPLC pump or equivalent), whereupon the column is purged with dry toluene (J.T. Baker, 0.2 mL/min), before pumping (0.2 mL/min) a solution of POS Ic from Example 1 (0.8 g per gram of particle mixture) and water (0.04 mL per gram of particle mixture) that is pre-diluted in toluene. These reactions can use short (less than 1 hour) or extended flow times (less than 72 hours) to aid in monolith formation. The column pressure is allowed to drop for 30 minutes prior to disconnection. The columns are left uncapped in a chemical fume hood's air stream for 5-18 hours, transferred to a 65°C convection oven for 28 hours and then cooled to room temperature. Analysis of these hybrid monoliths (SSA, SPV, APD, %C, SEM, mercury porosimetry) is performed on samples that are extruded from the columns and are vacuum dried for a minimum of 8 hours at room temperature.

This monolith formation of hybrid inorganic/organic particles is performed using a variety of hybrid inorganic/organic POS from Example 1 (Ia-Ix), nanoparticle containing POS from Example 12, or sub-1 μm particle containing POS as detailed in Example 24. To increase the macropore volume of this monolith, the silica template may be removed through purging the column with solutions of aqueous sodium hydroxide or trimethyl amine. Alternatively, the silica particle may be replaced with appropriately sized polystyrene latex. For this alternative monolith system, solvents that do not swell or dissolve the polystyrene latex must be employed (e.g., a polar protic solvent, or the pumping of a POS from Example 1 with or without additional water present). Upon formation of the coalesced hybrid particle monolith, the polystyrene particles can be removed thermally or by purging the column with toluene. Thermal removal of polystyrene can be aided with an inert atmosphere purge (nitrogen or argon) or the use of vacuum.

EXAMPLE 38 Hydrothermal Processing of Surrounded Hybrid Monoliths A monolith from Examples 36 or 37 is mixed with an aqueous solution of 0.3 M tris(hydroxymethyl)aminomethane (TRIS, Aldrich Chemical, Milwaukee, WI) at a concentration of 5 mL/g, and the pH is adjusted to 9.8 using acetic acid (J.T. Baker, Phillipsburgh, NJ). The monolith is enclosed in a stainless steel autoclave and is heated to 155 ⁰C for 20 hours. After cooling the autoclave to room temperature, the product is washed with water and methanol (Fisher Scientific, Suwanee, GA), and is dried at 80 ⁰C under vacuum for 16 hours. Products prepared in this manner have chromatographically enhanced pore geometry.

EXAMPLE 39

Surface Modification of Surrounded Hybrid Monoliths

A monolith from Examples 36, 37 or 38 is treated with a 1 molar hydrochloric acid solution

(Aldrich, Milwaukee, WI) for 20 h at 98°C. After cooling the product is washed with water to a neutral pH, followed by acetone (HPLC grade, Fisher Scientific, Fairlawn, NJ.). The monolith is dried at 80⁰C under vacuum for 16 h. Surface silanol groups of these surrounded hybrid monoliths can be modified in a similar manner as shown in Examples 20-22 by reaction with chlorosilanes. Hybrid monoliths containing surface hydroxypropyl groups can be modified in a similar manner as shown in Example 18- 19 by reaction with isocyanates. Other transformations of synthetically relevant hybrid groups have been reported in US patent No. 7,250,214. Chromatographic evaluation of surface modified hybrid monoliths having a surrounding material prepared in chromatographic columns can be performed in a similar manner as detailed in Examples 27-30. Chemical stability tests can also be performed as detailed in Examples 31-32.

EXAMPLE 40 Reaction of Bonded Hybrid Particles with Isocyanates Following the procedure in Example 26, products 25g and 25h were reacted with octadecyl isocyanate, followed by endcapping with trimethylchlorosilane. Product data is shown in Table 34.

Table 34

EXAMPLE 41

Reaction of Bonded Hybrid Particles with Isocyanates

Following the general procedure in Example 26, product 25a-h reacts with 4-cyanophenyl isocyanate, 3-cyanophenyl isocyanate, or 2-cyanophenyl isocyanate. Hydrolysis type A, B, or C from Example 18 is preformed. Products prepared by this manner can be endcapped or used without any further transformation.

Incorporation By Reference

The entire contents of all patents published patent applications and other references cited herein are hereby expressly incorporated herein in their entireties by reference.

Equivalents Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, numerous equivalents to the specific procedures described herein. Such equivalents are considered to be within the scope of this invention and are covered by the following claims.

Claims

What is claimed is:

1. An inorganic/organic hybrid material comprising an inorganic/organic hybrid surrounding material and an inorganic/organic hybrid core.

2. The inorganic/organic hybrid material of claim 1, wherein the inorganic/organic hybrid surrounding material and the inorganic/organic hybrid core are composed of different materials.

3. The inorganic/organic hybrid material of claim 1, wherein the inorganic/organic hybrid surrounding material and the inorganic/organic hybrid core are composed of the same materials.

4. The inorganic/organic hybrid material of claim 1, wherein the inorganic/organic hybrid surrounding material is composed of a material which enhances one or more of the characteristics selected from the group consisting of chromatographic selectivity, column chemical stability, column efficiency, and mechanical strength.

5. The inorganic/organic hybrid material of claim 1, wherein the inorganic/organic hybrid core is composed of a material which enhances one or more characteristics selected from the group consisting of chromatographic selectivity, column chemical stability, column efficiency, and mechanical strength.

6. The inorganic/organic hybrid material of claim 4, wherein the porous inorganic/organic surrounding material is composed of a material which provides advantages in chromatographic separation.

7. The inorganic/organic hybrid material of claim 5, wherein the inorganic/organic hybrid core is composed of a material which provides advantages in chromatographic separation.

8. The inorganic/organic hybrid material of claim 4, wherein the inorganic/organic surrounding material is composed of a material which provides a change in hydrophilic/lipophilic balance (HLB), surface charge (e.g., isoelectric point or silanol pKa), and/or surface functionality for enhanced chromatographic separation.

9. The inorganic/organic hybrid material of claim 1, wherein the inorganic/organic surrounding material is derived from condensation of one or more polymeric organo functional metal precursors, and/or polymeric metal oxide precursors on the surface of the hybrid 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 the surface of the hybrid core.

10. The inorganic/organic hybrid material of claim 9, wherein the inorganic portion of the inorganic/organic surrounding material is selected from the group consisting of alumina, silica, titania, cerium oxide, or zirconium oxides, and ceramic materials.

11. The inorganic/organic hybrid material of claim 10, wherein the inorganic portion of the inorganic/organic surrounding material is silica.

12. 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 of the 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 hybrid core.

13. The inorganic/organic hybrid material of claim 1 , wherein the hybrid content of the inorganic/organic surrounding material ranges from about 0-100 mol% hybrid.

14. The inorganic/organic hybrid material of claim 1, wherein the inorganic/organic surrounding material is independently selected from alumina, silica, titanium oxide, zirconium oxide and ceramic materials.

15. The inorganic/organic hybrid material of claim 1, wherein the inorganic/organic surrounding material is silica.

16. The inorganic/organic hybrid material of claim 1, wherein the structure of the inorganic/organic surrounding material comprises a copolymeric structure.

17. The inorganic/organic hybrid material of claim 1, wherein the pore structure of the inorganic/organic surrounding material comprises an ordered pore structure.

18. The inorganic/organic hybrid material of claim 17, wherein the inorganic portion of the inorganic/organic surrounding material is present in an amount ranging from about 0 molar % to not more than about 25 molar %, wherein the pores of the inorganic/organic surrounding material are substantially disordered.

19. The hybrid material of claim 17, wherein the inorganic portion of the inorganic/organic surrounding material is present in an amount ranging from about 25 molar % to not more than about 50 molar %, wherein the pores of the inorganic/organic surrounding material are substantially disordered, and wherein the inorganic/organic surrounding material possesses a chromatographically enhancing pore geometry (CEPG).

20. The inorganic/organic hybrid material of claim 1 , wherein the inorganic portion of the inorganic/organic surrounding material is independently selected from the group consisting of alumina, silica, titanium oxide, cerium oxide, zirconium oxide and ceramic materials.

21. The inorganic/organic hybrid material of claim 17, comprising Siθ₂ in an amount ranging from about 0 molar % to not more than about 25 molar %, wherein the pores of the inorganic/organic surrounding material are substantially disordered.

22. The inorganic/organic hybrid material of claim 17, comprising Siθ₂ in an amount ranging from about 25 molar % to not more than about 50 molar %, wherein the pores of the inorganic/organic surrounding material are substantially disordered and wherein the material has a chromatographically enhancing pore geometry (CEPG).

23. The inorganic/organic hybrid material of claim 1, wherein the inorganic/organic surrounding material has a chromatographically enhancing pore geometry (CEPG).

24. The inorganic/organic hybrid material of claim 1, wherein the inorganic/organic surrounding material comprises a material of formula I: (SiO₂)_d/[R²((R)_p(R¹)_qSiO_t)_m]; (I) wherein,

R and R¹ are each independently CpCi₈ alkoxy, CpCi₈ alkyl, CpCi₈ alkyl, C₂-Qg alkenyl, C₂-Ci₈ alkynyl, C₃-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, C₅-Ci₈ aryloxy, or CpCi₈ heteroaryl; R is CpCi₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, C₃-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl,

C₅-Ci₈ aryl, CpCi₈ heteroaryl; or absent; wherein each R² 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, R¹ and R² are optionally substituted; provided that:

25. The inorganic/organic hybrid material of claim 1, wherein the inorganic/organic surrounding material comprises a material of formula II :

(SiO₂)_d/[(R)_p(R¹)_qSiO_t] (II); wherein, R and R¹ are each independently CpCi₈ alkoxy, CpCi₈ alkyl, CpCi₈ alkyl, C₂-C₁8 alkenyl,

C₂-Ci₈ alkynyl, C₃-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, C₅-Ci₈ aryloxy, or CpCi₈ heteroaryl; d is 0 to about 30; p and q are each independently 0.0 to 3.0, provided that when p+q=l then t=l .5; when p+q=2 then t= 1 ; or when p+q=3 then t=0.5.

26. The inorganic/organic hybrid material of claim 1, wherein the inorganic/organic surrounding material comprises a material of formula III:

(SiO₂)_d/[R²((R¹)_rSiO_t)_m] (III) wherein,

R¹ is CpCi₈ alkoxy, CpCi₈ alkyl, CpCi₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, C₃-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, C₅-Ci₈ aryloxy, or CpCi₈ heteroaryl;

27. The hybrid material of claim 1, wherein the inorganic/organic surrounding material comprises a material of 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.

28. The hybrid material of claim 1, wherein the inorganic/organic surrounding material comprises a material of formula V:

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 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.

29. The hybrid material of claim 24, wherein R² is absent.

30. The hybrid material of claim 24, wherein R² is present.

31. The hybrid material of claim 1 , wherein the inorganic/organic surrounding material is porous with ordered pore structure and having a chromatographically-enhancing pore geometry (CEPG).

32. The inorganic/organic hybrid material of claim 1, wherein the hybrid content of the inorganic/organic hybrid core ranges from 1-100 mol% hybrid.

33. The inorganic/organic hybrid material of claim 32, wherein the hybrid content of the inorganic/organic hybrid core ranges from 4- 100 mol% hybrid.

34. The inorganic/organic hybrid material of claim 32, wherein the structure of the inorganic/organic hybrid core is independently selected to possess or not possess a copolymeric structure.

35. The inorganic/organic hybrid material of claim 32, wherein the pore structure of the inorganic/organic hybrid core is independently selected to possess or not possess an ordered pore structure.

36. The inorganic/organic hybrid material of claim 1, wherein the inorganic/organic hybrid core is nonporous.

37. The inorganic/organic hybrid material of claim 1, wherein said inorganic/organic hybrid core is porous.

38. The inorganic/organic hybrid material of claim 37, wherein the inorganic portion of said inorganic/organic hybrid core is present in an amount ranging from about 0 molar % to not more than about 25 molar %, wherein the pores of the inorganic/organic hybrid core are substantially disordered.

39. The hybrid material of claim 37, wherein the inorganic portion of said inorganic/organic hybrid core is present in an amount ranging from about 25 molar % to not more than about 50 molar %, wherein the pores of the inorganic/organic hybrid core are substantially disordered and wherein the hybrid core has a chromatographically enhancing pore geometry (CEPG).

40. The inorganic/organic hybrid material of claim 38 or claim 39, wherein the inorganic portion of the inorganic/organic hybrid core is selected from the group consisting of alumina, silica, titanium oxide, zirconium oxide and ceramic materials.

41. The inorganic/organic hybrid material of claim 37, comprising Siθ₂ in an amount ranging from about 0 molar % to not more than about 25 molar %, wherein the pores of the inorganic/organic hybrid core are substantially disordered.

42. The inorganic/organic hybrid material of claim 37, comprising Siθ₂ in an amount ranging from about 25 molar % to not more than about 50 molar %, wherein the pores of the inorganic/organic hybrid core are substantially disordered and wherein the particle has a chromatographically enhancing pore geometry (CEPG).

43. The inorganic/organic hybrid material of claim 38 or claim 39, wherein the inorganic/organic hybrid core has a chromatographically enhancing pore geometry (CEPG).

44. The inorganic/organic hybrid material of claim 1, wherein the inorganic/organic hybrid core has formula I: (SiO₂)_d/[R²((R)_p(R¹)_qSiO_t)_m]; (I) wherein,

R and R¹ are each independently Ci-Ci₈ alkoxy, CpCi₈ alkyl, CpCi₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, Cs-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, C₅-Ci₈ aryloxy, or CpCi₈ heteroaryl; R² is CpCi₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, C₃-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl,

C₅-Ci₈ aryl, CpCi₈ heteroaryl; or absent; wherein each R 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, R¹ and R² are optionally substituted; provided that:

(1) when R is absent, m=l and t = (4-(p+q)), when 0<p+q < 3; and

2

(2) when R is present, m=2-20 and t = (3-(p+q)), when p+q < 2 .

2

45. The inorganic/organic hybrid material of claim 1, wherein the inorganic/organic hybrid core has formula II : (SiOzVKBQpCR^qSiOt] (II); wherein,

R and R¹ are each independently CpCi₈ alkoxy, CpCi₈ alkyl, CpCi₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, C₃-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, C₅-Ci₈ aryloxy, or CpCi₈ heteroaryl; d is 0 to about 30; p and q are each independently 0.0 to 3.0, provided that when p+q=l then t=l .5; when p+q=2 then t=l ; or when p+q=3 then t=0.5.

46. The inorganic/organic hybrid material of claim 1, wherein the inorganic/organic hybrid core has formula III:

(SiO₂)_d/[R²((R¹)_rSiO_t)_m] (III) wherein,

R¹ is Ci-Ci₈ alkoxy, Ci-Ci₈ alkyl, C_rCi₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, C₃-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, C₅-Ci₈ aryloxy, or CpCi₈ heteroaryl; R is CpCi₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, C₃-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl,

C₅-Ci₈ aryl, CpCi₈ heteroaryl; or absent; wherein each R² 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=l .5; or when r=l then t=l ; or when r=2 then t=0.5; and m is an integer from 1 -20.

47. The inorganic/organic hybrid material of claim 41 or claim 42, wherein the inorganic/organic hybrid core has formula IV:

48. The inorganic/organic hybrid material of claim 41 or claim 42, wherein the inorganic/organic hybrid core has formula V:

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 (i.e., polymerizable) 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 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.

49. The inorganic/organic hybrid material of claim 44 wherein R² is absent.

50. The inorganic/organic hybrid material of claim 44, wherein R² is present.

51. The inorganic/organic hybrid material of claim 41 , wherein said inorganic/organic hybrid core is porous with ordered pore structure and having a chromatographically-enhancing pore geometry (CEPG).

52. The inorganic/organic hybrid material of claim 1, wherein the inorganic/organic hybrid core and/or the inorganic/organic surrounding material is a porous hybrid inorganic/organic material comprising ordered domains having formula IV, V or VI below:

C is an inorganic repeat unit which is bonded to one or more repeat units B or C via an inorganic bond; and x, 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;

(A)_x(B)_y(B*)_y*(C)_z (_Formui_{a V}) wherein the order of repeat units A, B, B*, and C may be random, block, or a combination of random and block;

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, 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; or

[A]_y[B]_x (Formula VI), wherein x and y are whole number integers and A is SiO₂/(R¹ _pR² _qSiO_t)_n or SiO₂/[R³(R¹ _rSiO_t)_m]_n; wherein R¹ and R² are independently a substituted or unsubstituted Ci to C₇ alkyl group, or a substituted or unsubstituted aryl group, R³ is a substituted or unsubstituted Ci to C₇ alkyl, alkenyl, alkynyl, or arylene group bridging two or more silicon atoms, p and q are 0, 1 , or 2, provided that p + q = 1 or 2, and that when p + q = 1, t = 1.5, and when p + q = 2, t = 1; r is 0 or 1, provided that when r = 0, t = 1.5, and when r = 1 , t = 1 ; m is an integer greater than or equal to 2; and n is a number from 0.01 to 100;

B is : SiO₂/(R⁴vSiO_t)_n wherein R⁴ is hydroxyl, fluorine, alkoxy, aryloxy, substituted siloxane, protein, peptide, carbohydrate, nucleic acid, or combinations thereof, R⁴ is not R¹, R², or R³; v is 1 or 2, provided that when v = 1 , t = 1.5, and when v=2, t =1 ; and n is a number from 0.01 to 100; wherein the material of formula VI has an interior area and an exterior surface, and said interior area of said material has a composition represented by A; said exterior surface of said material has a composition represented by A and B, and wherein said exterior composition is between about 1 and about 99% of the composition of B and the remainder comprising A.

53. The inorganic/organic hybrid material of claim 52 wherein diffraction peak maxima observed for said material of formula IV, V or VI, exhibit a 2Θ position that excludes diffraction peaks resulting from atomic-range order that are associated with amorphous material.

54. The inorganic/organic hybrid material of claim 53, wherein the excluded diffraction peak ranges from about 20° to about 23° 2Θ.

55. The inorganic/organic hybrid material of claim 52, wherein said inorganic portion of said inorganic/organic hybrid material of formula IV, V or VI is selected from the group consisting of alumina, silica, titania, cerium oxide, or zirconium oxides, and ceramic materials.

56. The inorganic/organic hybrid material of claim 55, wherein said inorganic portion of said inorganic/organic hybrid material is silica.

57. The inorganic/organic hybrid material of claim 52, wherein the percentage by mass of ordered domains of said inorganic/organic material ranges from about 1% to about 100%.

58. The inorganic/organic hybrid material of claim 1, wherein said inorganic/organic hybrid core is porous, wherein the pores of the inorganic/organic hybrid core are substantially disordered and wherein the inorganic/organic hybrid core has a chromatographically enhancing pore geometry (CEPG).

59. The inorganic/organic hybrid material of claim 1, wherein the inorganic/organic hybrid core is a monolith.

60. The inorganic/organic hybrid material of claim 1, wherein the hybrid core is a particle.

61. The inorganic/organic hybrid material of claim 60, wherein the particles are spherical.

62. The inorganic/organic hybrid material of claim 61, wherein the spherical particle has a noncrystalline or amorphous molecular ordering.

63. The inorganic/organic hybrid material of claim 61, wherein the spherical particle has a non- periodic pore structure.

64. The inorganic/organic hybrid material of claim 1, wherein the inorganic/organic hybrid

2 material has a surface area of about 40 to 1100 m Ig.

65. The inorganic/organic hybrid material of claim 64, wherein the inorganic/organic hybrid

2 material has a surface area of about 80 to 500 m /g.

66. The inorganic/organic hybrid material of claim 64, wherein the inorganic/organic hybrid

2 material has a surface area of about 800 to 1100 m /g.

67. The inorganic/organic hybrid material of claim 1 , wherein the hybrid core material has micropore volumes of about 0.2 to 1.5 cm /g.

68. The hybrid material of claim 67, wherein the inorganic/organic hybrid material has

3 micropore volumes of about 0.6 to 1.3 cm Ig.

69. The inorganic/organic hybrid material of claim 1, wherein the inorganic/organic hybrid material has a micropore surface area of less than about 110 m²/g.

70. The inorganic/organic hybrid material of claim 69, wherein the inorganic/organic hybrid material has a micropore surface area of less than about 105 m Ig.

71. The inorganic/organic hybrid material of claim 69, wherein the inorganic/organic hybrid material has a micropore surface area of less than about 80 m²/g.

72. The inorganic/organic hybrid material of claim 69, wherein the inorganic/organic hybrid material has a micropore surface area of less than about 50 m Ig.

73. The inorganic/organic hybrid material of claim 1, wherein the inorganic/organic hybrid material has an average pore diameter of about 20 to 1 OOOA.

74. The inorganic/organic hybrid material of claim 73, wherein the inorganic/organic hybrid material has an average pore diameter of about 30 to 3OθA.

75. The inorganic/organic hybrid material of claim 1, wherein the inorganic/organic hybrid material has an average pore diameter of about 60 to 2OθA.

76. The inorganic/organic hybrid material of claim 75, wherein the inorganic/organic hybrid material has an average pore diameter of about 80 to 140A.

77. The inorganic/organic hybrid material of clam 1, wherein the inorganic/organic hybrid material has an average size of about 0.1 μm to about 300 μm.

78. The inorganic/organic hybrid material of claim 76, wherein the inorganic/organic hybrid material has an average size of about 0.1 μm to about 30 μm.

79. The inorganic/organic hybrid material of claim 1, wherein the inorganic/organic hybrid material is hydro lytically stable at a pH of about 1 to about 14.

80. The inorganic/organic hybrid material of claim 79, wherein the inorganic/organic hybrid material is hydro lytically stable at a pH of about 10 to about 14.

81. The inorganic/organic hybrid material of claim 79, wherein the inorganic/organic hybrid material is hydro lytically stable at a pH of about 1 to about 5.

82. The inorganic/organic hybrid material of claim 1, wherein the organic content is from about 10 to about 40% carbon.

83. The inorganic/organic hybrid material of claim 1, wherein the organic content is from about 25 to about 40% carbon.

84. The inorganic/organic hybrid material of claim 1, wherein the organic content is from about 15 to about 35% carbon.

85. The inorganic/organic hybrid material of claim 83, wherein the organic content is from about 25 to about 35% carbon.

86. The inorganic/organic hybrid material of claim 24, 25, 44 or 45, wherein R is CpCi₈ alkoxy, Ci-Ci₈ alkyl, or C₁-C₁₈ alkyl.

87. The inorganic/organic hybrid material of claim 24, 25, 26, 44, 45 or 46 , wherein R¹ is Cp Ci₈ alkoxy, CpCi₈ alkyl, or CpCi₈ alkyl.

88. The inorganic/organic hybrid material of claim 24, 26, 44 or 46 wherein R² is CpCi₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, Cs-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, or CpCi₈ heteroaryl.

89. The inorganic/organic hybrid material of claim 24 or 44, wherein p is 0, q is 0, t is 1.5, m is 2, and R is CpCi₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, Cs-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl,

C₅-Ci₈ aryl, or CpCi₈ heteroaryl; and wherein each R² is attached to two or more silicon atoms.

90. The inorganic/organic hybrid material of claim 89, wherein d is 0.

91. The inorganic/organic hybrid material of claim 89, wherein d is 0.11.

92. The inorganic/organic hybrid material of claim 89, wherein d is 0.33.

93. The inorganic/organic hybrid material of claim 89, wherein d is 0.83.

94. The inorganic/organic hybrid material of claim 24 or 44, wherein d is 0, q is 0, and R² is Cp Ci₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, Cs-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, or CpCi₈ heteroaryl; and wherein each R² is attached to two or more silicon atoms.

95. The inorganic/organic hybrid material of claim 94, wherein p is 0, 1, or 2.

96. The inorganic/organic hybrid material of claim 94, wherein t is 1.0 or 1.5.

97. The inorganic/organic hybrid material of claim 94, wherein m is 1 or 2.

98. The inorganic/organic hybrid material of claim 1, wherein the inorganic/organic hybrid core is formed by hydro lytic condensation of one or more monomers selected from the group consisting of:

wherein

R, R¹ and R² are as defined in claim 24; X is C₁-C₁8 alkoxy or CpCig alkyl; and n is 1-8.

99. The inorganic/organic hybrid material of claim 98, wherein the monomer is 1 ,2- bis(triethoxysilyl)ethane:

100. The inorganic/organic hybrid material of claim 98, wherein the monomer is 1 ,2- bis(methyldiethoxy silyl)ethane:

or 1,8- bis(triethoxysilyl)octane:

101. The inorganic/organic hybrid material of claim 1 , wherein said inorganic/organic hybrid material has been surface modified with a surface modifier having the formula Z_a(R')bSi-R", where Z = Cl, Br, I, Cl - C5 alkoxy, dialkylamino or trifluoromethanesulfonate; a and b are each an integer from 0 to 3 provided that a + b = 3; R' is a Cl - Ce straight, cyclic or branched alkyl group, and R" is a functionalizing group.

102. The inorganic/organic hybrid material of claim 1, wherein said inorganic/organic hybrid material has been surface modified by coating with a polymer.

103. The inorganic/organic hybrid material of claim 101 wherein R' is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, t-butyl, sec-butyl, pentyl, isopentyl, hexyl and cyclohexyl.

104. The inorganic/organic hybrid material of claim 101, wherein the functionalizing group R is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, cyano, amino, diol, nitro, ester, a cation or anion exchange group, an alkyl or aryl group containing an embedded polar functionality and a chiral moiety.

105. The inorganic/organic hybrid material of claim 103, wherein said functionalizing group R" is a Cl - C30 alkyl group.

106. The inorganic/organic hybrid material of claim 103, wherein said functionalizing group R" comprises a chiral moiety.

107. The inorganic/organic hybrid material of claim 104, wherein said functionalizing group R" is a Cl - C20 alkyl group.

108. The hybrid material of claim 103, wherein said surface modifier is selected from the group consisting of octyltrichlorosilane, octadecyltrichlorosilane, octyldimethylchlorosilane and octadecyldimethylchlorosilane.

109. The inorganic/organic hybrid material of claim 103, wherein said surface modifier is selected from the group consisting of octyltrichlorosilane and octadecyltrichlorosilane.

110. The inorganic/organic hybrid material of claim 1, wherein said inorganic/organic hybrid material have been surface modified by a combination of organic group and silanol group modification.

111. The hybrid material of claim 111, wherein said inorganic/organic hybrid material have been surface modified by a combination of organic group modification and coating with a polymer.

112. The inorganic/organic hybrid material of claim 111, wherein said organic group comprises a chiral moiety.

113. The hybrid material of claim 101, wherein said inorganic/organic hybrid material have been surface modified by a combination of silanol group modification and coating with a polymer.

114. The inorganic/organic hybrid material of claim 101, wherein said inorganic/organic hybrid material have been surface modified via formation of an organic covalent bond between the material's organic group and the modifying reagent.

115. The inorganic/organic hybrid material of claim 101, wherein said inorganic/organic hybrid material have been surface modified by a combination of organic group modification, silanol group modification and coating with a polymer.

116. The inorganic/organic hybrid material of claim 101, wherein said inorganic/organic hybrid material have been surface modified by silanol group modification.

117. The porous inorganic/organic hybrid material of claim 1, wherein said inorganic/organic hybrid material has been surface modified by organic group modification.

118. The porous inorganic/organic hybrid material of claim 117, wherein said inorganic/organic hybrid material have been surface modified by a combination of organic group and silanol group modification.

119. The porous inorganic/organic hybrid material of claim 1 , further comprising a nanoparticle dispersed within the material.

120. The composite material of claim 119, wherein nanoparticle is a mixture of more than one nanoparticle.

121. The composite material of claim 119, wherein the nanoparticle is present in <20% by weight of the nanocomposite.

122. The composite material of claim 119, wherein the nanoparticle is present in <5% by weight of the nanocomposite.

123. The composite material of claim 119, wherein the nanoparticle is crystalline or amorphous.

124. The composite material of claim 119 or 120, wherein the nanoparticle is a substance which comprises one or more moieties selected from the group consisting of silicon carbide, aluminum, diamond, cerium, carbon black, carbon nanotubes, zirconium, barium, cerium, cobalt, copper, europium, gadolinium, iron, nickel, samarium, silicon, silver, titanium, zinc, boron, oxides thereof, and nitrides thereof.

125. The composite material of claim 124, wherein the nanoparticle is a substance which comprises one or more moieties selected from the group consisting of nano-diamonds, silicon carbide, titanium dioxide, cubic-boronitride.

126. The composite material of claim 119 or 120, wherein the nanoparticles are less than or equal to 200 μm in diameter.

127. The composite material of claim 119 or 120, wherein the nanoparticles are less than or equal to 100 μm in diameter.

128. The composite material of claim 119 or 120, wherein the nanoparticles are less than or equal to 50 μm in diameter.

129. The composite material of claim 119 or 120, wherein the nanoparticles are less than or equal to 20 μm in diameter.

130. An inorganic/organic hybrid particle comprising an inorganic/organic hybrid particle core and an inorganic/organic surrounding material wherein said particle has the formula

(Y(CH₂)_nSiOi _S)_x(O₁5SiCH₂CH₂SiOi ₅)_y(Si0₂)_z wherein: each Y is independently -OH, -NH₂, -NR₂, -NR₂R⁵⁺, SH, S(OV₂R, S(OV₂O^", CpCi₈ alkoxy, Ci-Ci₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, C₃-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, C₅-Ci₈ aryloxy, or CpCi₈ heteroarylaryl, CpCi₈ alkoxy, CpCi₈ alkyl, CpCi₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, C₃-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, C₅-Ci₈ aryloxy, or CpCi₈ heteroaryl; each R and R are independently CpCi₈ alkoxy, CpCi₈ alkyl, CpCi₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, C₃-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, C₅-Ci₈ aryloxy, or CpCi₈ heteroaryl; n is from 0 to 18; and x, y and z are independently from about 0.0 to about 1.0 wherein y+z is 1.0-x and y is from about 3.0 to about 5.0 times greater than z.

131. A method for preparing an inorganic/organic hybrid material comprising an inorganic/organic hybrid core and an inorganic/organic surrounding material comprising the steps of: providing an inorganic/organic hybrid core material; and

condensing one or more polymeric organofunctional metal precursors, and/or polymeric metal oxide precursors on the surface of the inorganic/organic hybrid core.

132. A method for preparing an inorganic/organic hybrid material comprising an inorganic/organic hybrid core and an inorganic/organic surrounding material comprising the steps of: providing an inorganic/organic hybrid core material;

applying a 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 on the surface of the hybrid core; and further condensing said surface.

133. The method of claim 131 or 132, further comprising the step of subjecting the hybrid core material to hydrothermal treatment.

134. The method of claim 133, further comprising the step of surface modification.

135. The method of claim 131 or 132, wherein the hybrid core material is a particle.

136. A method for producing an inorganic/organic hybrid material comprising an inorganic/organic hybrid core and an inorganic/organic surrounding material comprising the steps of: providing an inorganic/organic hybrid core material; and

condensing one or more polymeric organofunctional metal precursors, and/or polymeric metal oxide precursors on the surface of the hybrid core, to thereby produce an hybrid material of any one of claims 1-130.

137. A method for producing an inorganic/organic hybrid material comprising an inorganic/organic hybrid core and an inorganic/organic surrounding material of any one of claims 1- 130 comprising the steps of: providing an inorganic/organic hybrid core material;

applying a 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 on the surface of the hybrid core; and further condensing said surface, to thereby produce an hybrid material of any one of claims 1-130.

138. The method of claim 136 or 137, further comprising the step of subjecting the hybrid core material to hydrothermal treatment.

139. The method of claim 138, further comprising the step of surface modification.

140. The method of claim 136 or 137, further comprising the step of dispersing a nanoparticle within the hybrid material.

141. The method of claim 140, wherein nanoparticle is a mixture of more than one nanoparticle.

142. The method of claim 140, wherein the nanoparticle is present in <20% by weight of the nanocomposite.

143. The method of claim 140, wherein the nanoparticle is present in <5% by weight of the nanocomposite.

144. The method of claim 140, wherein the nanoparticle is crystalline or amorphous.

145. The method of claim 140 or 141, wherein the nanoparticle is a substance which comprises one or more moieties selected from the group consisting of silicon carbide, aluminum, diamond, cerium, carbon black, carbon nanotubes, zirconium, barium, cerium, cobalt, copper, europium, gadolinium, iron, nickel, samarium, silicon, silver, titanium, zinc, boron, oxides thereof, and nitrides thereof.

146. The method of claim 145, wherein the nanoparticle is a substance which comprises one or more moieties selected from the group consisting of nano-diamonds, silicon carbide, titanium dioxide, cubic-boronitride.

147. The method of claim 140 or 141, wherein the nanoparticles are less than or equal to 200 μm in diameter.

148. The method of claim 140 or 141, wherein the nanoparticles are less than or equal to 100 μm in diameter.

149. The method of claim 140 or 141, wherein the nanoparticles are less than or equal to 50 μm in diameter.

150. The method of claim 140 or 141, wherein the nanoparticles are less than or equal to 20 μm in diameter.

151. The method of claim 136 or 137, wherein the inorganic/organic hybrid core material is a particle.

152. The method of claim 136 or 137, wherein the inorganic/organic hybrid core material is provided by the steps of: a) hydrolytically condensing one or more monomers selected from the group consisting of organoalkoxysilanes and tetraalkoxysilanes, with one or more monomers selected from the group consisting of organoalkoxysilanes, tetraalkoxysilanes, metal oxide precursors and ceramic precursors, to produce a polyorganoalkoxysiloxane; b) further condensing the polyorganoalkoxysiloxane to form a spherical porous particle; and c) subjecting the resulting particle to hydrothermal treatment; to thereby produce a porous inorganic/organic hybrid core material.

153. The method of claim 152 for producing a porous inorganic/organic hybrid particle of claim 1 , wherein said one or more monomers exclude tetraalkoxysilanes.

154. The method of claim 152, wherein the metal oxide precursors are selected from the group consisting of the oxide, hydroxide, ethoxide, methoxide, propoxide, isopropoxide, butoxide, sec- butoxide, tert-butoxide, iso-butoxide, phenoxide, ethylhexyloxide, 2-methyl-2-butoxide, nonyloxide, isooctyloxide, glycolates, carboxylate, nitrate, chlorides, and mixtures thereof of titanium, zirconium, and aluminum.

155. The method of claim 154, wherein the metal oxide precursors are methyl titanium triisopropoxide, methyl titanium triphenoxide, titanium allylacetoacetatetriisopropoxide, titanium methacrylate triisopropoxide, titanium methacryloxyethylacetoacetate triisopropoxide, pentamethylcyclopentadienyl titanium trimethoxide, pentamethylcyclopentadienyl titanium trichloride, or zirconium methacryloxyethylacetoacetate tri-n-propoxide.

156. The method of claim 136 or 137, wherein the inorganic/organic hybrid core material is provided by the steps of: a) hydrolytically condensing one or more monomers selected from the group consisting of organoalkoxysilanes and tetraalkoxysilanes, to produce a polyorganoalkoxysiloxane; b) further condensing the polyorganoalkoxysiloxane to form a spherical porous particle; and c) subjecting the resulting particle to hydrothermal treatment; to thereby produce a porous inorganic/organic hybrid core material.

157. The method of claim 156 for producing a porous inorganic/organic hybrid core of claim Ia, wherein said one or more monomers exclude tetraalkoxysilanes.

158. The method of claim 152 or 156, wherein said condensing step comprises treating an aqueous emulsion of the polyorganoalkoxysiloxane with base to form a spherical particle.

159. The method of claim 158, further comprising treating the spherical porous particle with acid.

160. The method of claim 158, further comprising treating the aqueous emulsion of the polyorganoalkoxysiloxane with one or more additional aliquots of base to form a spherical particle.

161. The method of claim 160, further comprising treating the spherical porous particle with acid.

162. The method of claim 152 or 156, wherein the particle has a chromatographically enhancing pore geometry (CEPG).

163. The method of any one of claims 152-163, wherein the porous inorganic/organic hybrid particle has formula I, II, or III, as recited in claim 24, 25, or 26, respectively.

164. The method of any of claims 152-163, further comprising preparing an aqueous suspension of said polyorganoalkoxysiloxane and gelling in the presence of a base catalyst to produce the porous inorganic/organic hybrid particle.

165. The method of any one of claims 152-163, wherein step a) or step b) is acid-catalyzed or base-catalyzed.

166. The method of claim 165, wherein step a) is acid-catalyzed.

167. The method of claim 166, wherein the acid is selected from the group consisting of hydrochloric acid, hydrobromic acid, hydrofluoric acid, hydroiodic acid, sulfuric acid, formic acid, acetic acid, trichloroacetic acid, trifluoroacetic acid and phosphoric acid.

168. The method of claim 165, wherein step b) is base-catalyzed.

169. The method of claim 168, wherein the base is selected from the group consisting of alkyl amines, ammonium hydroxide, hydroxide salts of the group I and group II metals, carbonate and hydrogen carbonate salts of the group I metals and alkoxide salts of the group I and group II metals.

170. The method of claim 168, wherein the base-catalyzed reaction is an oil-in- water emulsification reaction.

171. The method of any one of claims 152-163, wherein steps a) and b) are performed in a solvent selected from the group consisting of water, methanol, ethanol, propanol, isopropanol, butanol, tert- butanol, pentanol, hexanol, cyclohexanol, hexafluoroisopropanol, cyclohexane, petroleum ethers, diethyl ether, dialkyl ethers, tetrahydrofuran, acetonitrile, ethyl acetate, pentane, hexane, heptane, benzene, toluene, xylene, N,N-dimethylformamide, dimethyl sulfoxide, 1 -methyl-2-pyrrolidinone, methylene chloride, chloroform, and combinations thereof.

172. The method of claim 136 or 137, wherein the inorganic/organic hybrid core material is provided by the steps of:

173. The method of claim 136 or 137, wherein the inorganic/organic material is provided by the steps of:

(b) hydro lyrically condensing the product of step (a) with a tetraalkoxysilane in the presence of a non-optically active porogen; and

(c) further condensing the product of step (b) to form a spherical porous particle.

174. The method of claim 172 or 173 wherein said copolymerizing step is free radical-initiated and wherein said hydro lyrically condensing step is an acid- or base-catalyzed.

175. The method of claim 172 or 173 , further comprising subjecting the resulting particle to hydrothermal treatment.

176. The method of any one of claims 152- 175, wherein the spherical porous particles produced in step b) or step c) are sized to generate a particle size distribution that is distinct from the particle size distribution of the spherical porous particles produced in step b) or step c).

177. The method of any one of claims 152- 175, wherein the spherical particle has a noncrystalline or amorphous molecular ordering.

178. The method of claim 177, wherein the spherical particle has a non-periodic pore structure.

179. The method of any one of claims 152-175, wherein said particle has a surface area of about 40 to l l00 m²/g.

2

180. The method of claim 179, wherein said particle has a surface area of about 80 to 500 m Ig.

181. The method of claim 179, wherein said particle has a surface area of about 800 to 1100 m /g.

182. The method of any one of claims 152- 175, wherein said particle has micropore volumes of about 0.2 to 1.5 cm³/g.

183. The method of claim 182, wherein said particle has micropore volumes of about 0.6 to 1.3 cm /g.

184. The method of any one of claims 152- 175, wherein said particle has a micropore surface area of less than about 110 m /g.

185. The method of claim 184, wherein said particle has a micropore surface area of less than about 105 m²/g.

186. The method of claim 184, wherein said particle has a micropore surface area of less than about 80 m /g.

187. The method of claim 184, wherein said particle has a micropore surface area of less than about 50 m²/g.

188. The method of any one of claims 152, 156, or 172, wherein said particle has an average pore diameter of about 20 to 5OθA.

189. The method of claim 187, wherein said particle has an average pore diameter of about 30 to 180A.

190. The method of any one of claims 152, 156, or 172, wherein said particle has an average pore diameter of about 60 to 200A.

191. The method of claim 190, wherein said particle has an average pore diameter of about 80 to 140 A.

192. The method of any one of claims 152- 191, wherein said particle has an average size of about 0.1 μm to about 300 μm.

193. The method of claim 192, wherein said particle has an average size of about 0.1 μmto about 30 μm.

194. The method of any one of claims 152- 191, wherein said particle is hydrolytically stable at a pH of about 1 to about 14.

195. The method of claim 194, wherein said particle is hydrolytically stable at a pH of about 10 to about 14.

196. The method of claim 194, wherein said particle is hydrolytically stable at a pH of about 1 to about 5.

197. The method of any one of claims 152- 191, wherein the organic content is from about 25 to about 40% carbon.

198. The method of claim 197, wherein the organic content is from about 25 to about 35% carbon.

199. The method of claim 152, wherein R is CpCi₈ alkoxy, CpCi₈ alkyl, or CpCi₈ alkyl.

200. The method of claim 152, wherein R¹ is CpCi₈ alkoxy CpCi₈ alkyl, or CpCi₈ alkyl.

201. The method of claim 152, wherein R² is CpCi₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, C₃-Ci₈ cycloalkyl, CpCi₈ heterocycloalkyl, C₅-Ci₈ aryl, or CpCi₈ heteroaryl.

202. The method of claim 152, wherein the porous inorganic/organic hybrid particle has formula I; wherein p is 0, q is 0, t is 1.5, m is 2, and R² is CpCi₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, C₃-Ci₈ cycloalkyl, Ci-Ci₈ heterocycloalkyl, C₅-Ci₈ aryl, or CpCi₈ heteroaryl; wherein each R² is attached to two or more silicon atoms.

203. The method of claim 202, wherein d is 0.

204. The method of claim 202, wherein d is 0.11.

205. The method of claim 202, wherein d is 0.33.

206. The method of claim 202, wherein d is 0.83.

207. The method of claim 152, wherein the porous inorganic/organic hybrid particle has formula I; wherein d is 0, q is 0, and R² is CpCi₈ alkyl, C₂-Ci₈ alkenyl, C₂-Ci₈ alkynyl, C₃-Ci₈ cycloalkyl, Cp Ci₈ heterocycloalkyl, C₅-Ci₈ aryl, or CpCi₈ heteroaryl; wherein each R is attached to two or more silicon atoms.

208. The method of claim 207, wherein p is 0, 1, or 2.

209. The method of claim 207, wherein t is 1.0 or 1.5.

210. The method of claim 207, wherein m is 1 or 2.

211. The method of any one of claims 152-191, wherein the one or more monomers are selected from the group consisting of:

wherein

R, R¹ and R² are as defined in claim 24; X is CpCi₈ alkoxy or CpCi₈ alkyl; and n is 1-8.

212. The method of claim 211, wherein the monomer is l,2-bis(triethoxysilyl)ethane:

213. The method of claim 211, wherein the monomer is 1 ,2-bis(methyldiethoxy silyl)ethane:

or 1,8- bis(triethoxysilyl)octane:

214. The method of any of claims 152- 191, wherein said particles have been surface modified with a surface modifier having the formula Z_a(R')bSi-R", where Z = Cl, Br, I, Cl - C5 alkoxy, dialkylamino or trifluoromethanesulfonate; a and b are each an integer from O to 3 provided that a + b = 3; R' is a Cl - Cβ straight, cyclic or branched alkyl group, and R" is a functionalizing group.

215. The method of claim 214, wherein said particles have been surface modified by coating with a polymer.

216. The method of claim 214 wherein R' is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, t-butyl, sec-butyl, pentyl, isopentyl, hexyl and cyclohexyl.

217. The method of claim 214, wherein the functionalizing group R" is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, cyano, amino, diol, nitro, ester, a cation or anion exchange group, an alkyl or aryl group containing an embedded polar functionality and a chiral moiety.

218. The method of claim 217, wherein said functionalizing group R" is a Cl - C30 alkyl group.

219. The method of claim 217, wherein said functionalizing group R" is a Cl - C20 alkyl group.

220. The method of claim 214, wherein said surface modifier is selected from the group consisting of octyltrichlorosilane, octadecyltrichlorosilane, octyldimethylchlorosilane and octadecyldimethylchlorosilane.

221. The method of claim 220, wherein said surface modifier is selected from the group consisting of octyltrichlorosilane and octadecyltrichlorosilane.

222. The method of claim 217, wherein said particles have been surface modified by a combination of organic group and silanol group modification.

223. The method of claim 217, wherein said particles have been surface modified by a combination of organic group modification and coating with a polymer.

224. The method of claim 217, wherein said particles have been surface modified by a combination of silanol group modification and coating with a polymer.

225. The method of claim 217, wherein said particles have been surface modified via formation of an organic covalent bond between the particle's organic group and the modifying reagent.

226. The method of claim 217, wherein said particles have been surface modified by a combination of organic group modification, silanol group modification and coating with a polymer.

227. The method of claim 217, wherein said particles have been surface modified by silanol group modification.

228. The method of any one of claims 152-191, wherein said porous inorganic/organic hybrid particles are modified by further including a porogen.

229. The method of claim 228, wherein said porogen is selected from the group consisting of cyclohexanol, toluene, mesitylene, 2-ethylhexanoic acid, dibutylphthalate, 1 -methyl-2-pyrrolidinone, 1-dodecanol and Triton X-45.

230. The method of claim 229, wherein said porogen is toluene or mesitylene.

231. The method of any one of claims 152-191, wherein said porous inorganic/organic hybrid particle resulting from step b) is modified by further including a surfactant or stabilizer.

232. The method of claim 231, wherein said surfactant is Triton X-45, Triton XlOO, Triton X305, TLS, Pluronic F-87, Pluronic P-105, Pluronic P-123, sodium dodecylsulfate (SDS), ammonia docecylsulfate, TRIS docecylsulfate, or Triton X- 165.

233. The method of claim 232, wherein said surfactant is sodium dodecylsulfate (SDS), ammonia docecylsulfate, or TRIS docecylsulfate.

234. An inorganic/organic hybrid material comprising an inorganic/organic hybrid core and an inorganic/organic exterior surface comprising Siθ₂ in an amount ranging from about 0 molar % to not more than about 25 molar %, wherein the pores of the particle are substantially disordered, produced by the method of any one of claims 131-233.

235. An inorganic/organic hybrid material comprising an inorganic/organic hybrid core and an inorganic/organic exterior surface comprising Siθ₂ in an amount ranging from about 25 molar % to not more than about 50 molar %, wherein the pores of the particle are substantially disordered and wherein the particle has a chromatographically enhancing pore geometry (CEPG), produced by the method of any one of claims 130-232.

236. The inorganic/organic hybrid material of claim 234, wherein the inorganic/organic hybrid core and inorganic/organic exterior surface has a chromatographically enhancing pore geometry (CEPG).

237. The inorganic/organic hybrid material of any one of claims 234-236, wherein the inorganic/organic hybrid core and the inorganic/organic exterior surface are independently selected from formula I, II, II, IV or V as recited in claim 24, 25, 26, 27 or 28, respectively

238. A separations device having a stationary phase comprising the inorganic/organic hybrid material of any one of claims 1-131.

239. The separations device of claim 238, 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.

240. The separations device of claim 239, 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.

241. 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 any one of claims 1-131.

242. A kit comprising the inorganic/organic hybrid material of any one of claims 1-131, and instructions for use.

243. The kit of claim 242, wherein the instructions are for use with a separations device.

244. The kit of claim 243, wherein the separations device is selected from the group consisting of chromatographic columns, thin layer plates, filtration membranes, sample cleanup devices and microtiter plates.

245. The method of any one of claims 132-134, wherein the porous inorganic/organic hybrid particle has formula IV or V as recited in claim 27 or claim 28, respectively.

246. The hybrid material of Claim 24, wherein R¹ is CpCig alkyl group substituted by hydroxyl.

247. The hybrid material of Claim 246, wherein R¹ is hydroxypropyl.

248. The hybrid material of Claim 246, wherein the hydroxy substituted alkyl group is further functionalized by an isocyanate.

249. The hybrid material of Claim 248, 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.