What is claimed is:
1. A porous inorganicorganic hybrid monolith material, comprising a chromatographically-enhancing pore geometry.
2. A porous inorganicorganic hybrid monolith material, wherein pores of a diameter of less than about 34 contribute less than about 100 m2g to less than about 50 m2g to the specific surface area of the material.
3. A porous inorganicorganic hybrid monolith material, comprising coalesced porous inorganicorganic hybrid particles having a chromatographically-enhancing pore geometry.
4. A porous inorganicorganic hybrid monolith material, comprising coalesced porous inorganicorganic hybrid particles that have a chromatographically-enhancing pore geometry, wherein said particles have been surface modified by a surface modifier selected from the group consisting of an organic group surface modifier, a silanol group surface modifier, a polymeric coating surface modifier, and combinations thereof,
5. The hybrid monolith material of claim 3, wherein said hybrid particles have been surface modified with a surface modifier having the formula Za(R)bSiR, where ZCl, Br, I, C1-C5 alkoxy, dialkylamino or trifluoromethanesulfonate; a and b are each an integer from 0 to 3 provided that ab3; R is a C1-C6 straight, cyclic or branched alkyl group, and R is a functionalizing group.
6. The hybrid monolith material of claim 3, wherein said hybrid particles have a specific surface area of about 50 to 800 m2g.
7. The hybrid monolith material of claim 3, wherein said hybrid particles have a specific surface area of about 75 to 600 m2g.
8. The hybrid monolith material of claim 3, wherein said hybrid particles have a specific surface area of about 100 to 350 m 2g.
9. The hybrid monolith material of claim 3, wherein said hybrid particles have specific pore volumes of about 0.25 to 1.5 cm3g.
10. The hybrid monolith material of claim 3, wherein said hybrid particles have specific pore volumes of about 0.4 to 1.2 cm3g.
11. The hybrid monolith material of claim 3, wherein said hybrid particles have a micropore surface area of less than about 110 m2g.
12. The hybrid monolith material of claim 11, wherein said hybrid particles have a micropore surface area of less than about 105 m2g.
13. The hybrid monolith material of claim 11, wherein said hybrid particles have a micropore surface area of less than about 80 m2g.
14. The hybrid monolith material of claim 11, wherein said hybrid particles have a micropore surface area of less than about 50 m2g.
15. The hybrid monolith material of claim 3, wherein said hybrid particles have an average pore diameter of about 50 to 500 .
16. The hybrid monolith material of claim 3, wherein said hybrid particles have an average pore diameter of about 100 to 300 .
17. The hybrid monolith material of claim 3, wherein said hybrid particles have a specific surface area of about 50 to 800 m2g, said hybrid particles have specific pore volumes of about 0.25 to 1.5 cm3g, and said hybrid particles have an average pore diameter of about 50 to 500 .
18. The hybrid monolith material of claim 3 or 4, wherein said hybrid particles have been surface modified by coating with a polymer.
19. The hybrid monolith material of claim 18, wherein said polymer is Sylgard.
20. The hybrid monolith material of claim 5, wherein R is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, t-butyl, sec-butyl, pentyl, isopentyl, hexyl and cyclohexyl.
21. The hybrid monolith material of claim 5, 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, or an alkyl or aryl group containing an embedded polar functionality.
22. The hybrid monolith material of claim 21, wherein said functionalizing group R is a C1-C30 alkyl group.
23. The hybrid monolith material of claim 21, wherein said functionalizing group R is a C1-C20 alkyl group.
24. The hybrid monolith material of claim 4, wherein said surface modifier is selected from the group consisting of octyltrichlorosilane, octadecyltrichlorosilane, octyldimethylchlorosilane, and octadecyldimethylchlorosilane.
25. The hybrid monolith material of claim 24, wherein said surface modifier is selected from the group consisting of octyltrichlorosilane and octadecyltrichlorosilane.
26. The hybrid monolith material of claim 3 or 4 having the formula SiO2(R2pR4qSiOt)n or SiO2R6(R2rSiOt)mn wherein R2 and R4 are independently C1-C18 aliphatic, styryl, vinyl, propanol, or aromatic moieties, R6is a substituted or unsubstituted C1-C18 alkylene, alkenylene, alkynylene or arylene moiety bridging two or more silicon atoms, p and q are 0, 1 or 2, provided that pq1 or 2, and that when pq1, t1.5, and when pq2, t1; r is 0 or 1, provided that when r0, t1.5, and when r1, t1; m is an integer greater than or equal to 2, and n is a number from 0.03 to 1.
27. The hybrid monolith material of claim 26, wherein n is a number from 0.1 to 1.
28. The hybrid monolith material of claim 26 having average pore diameters of about 100 to 300 .
29. The hybrid monolith material of claim 26 wherein n is a number from 0.20 to 0.5.
30. The hybrid monolith material of claim 3 or 4 wherein said inorganic portion of said hybrid monolith material is selected from the group consisting of alumina, silica, titanium or zirconium oxides, and ceramic materials.
31. The hybrid monolith material of claim 3 or 4 wherein said inorganic portion of said hybrid monolith material is silica.
32. The hybrid material of claim 3 or 4, wherein said particles have been surface modified by a combination of an organic group surface modifier and a silanol group surface modifier.
33. The hybrid material of claim 3 or 4, wherein said particles have been surface modified by a combination of an organic group surface modifier and a polymeric coating surface modifier.
34. The hybrid material of claim 3 or 4, wherein said particles have been surface modified by a combination of a silanol group surface modifier and a polymeric coating surface modifier.
35. The hybrid material of claim 3 or 4, wherein said particles have been surface modified via formation of an organic covalent bond between an organic group of the particle and a surface modifier.
36. The hybrid material of claim 3 or 4, wherein said particles have been surface modified by a combination of an organic group surface modifier, a silanol group surface modifier, and a polymeric coating surface modifier.
37. The hybrid material of claim 3 or 4, wherein said particles have been surface modified by a silanol group surface modifier.
38. A method of preparation of a porous inorganicorganic hybrid monolith material, comprising porous inorganicorganic hybrid particles having a chromatographically-enhancing pore geometry, comprising the steps of
a) forming porous inorganicorganic hybrid particles,
b) modifying the pore structure of said porous hybrid particles, and
c) coalescing said porous hybrid particles to form a monolith material.
39. The method of claim 38, wherein the porous hybrid particles are coalesced by sintering.
40. The method of claim 38, wherein the porous hybrid particles are mixed with a second material that is removed after coalescence of the porous hybrid particles.
41. The method of claim 40, wherein the second material is unbonded silica.
42. The method of claim 38, wherein said particles have been surface modified by a surface modifier selected from the group consisting of an organic group surface modifier, a silanol group surface modifier, a polymeric coating surface modifier, and combinations thereof.
43. The method of claim 38, wherein said particles have been surface modified by a polymeric coating surface modifier.
44. The method of claim 38, wherein said particles have been surface modified by a combination of an organic group surface modifier and a silanol group surface modifier.
45. The method of claim 38, wherein said particles have been surface modified by a combination of an organic group surface modifier and a polymeric coating surface modifier.
46. The method of claim 38, wherein said particles have been surface modified by a combination of a silanol group surface modifier and a polymeric coating surface modifier.
47. The method of claim 38, wherein said particles have been surface modified by a combination of an organic group surface modifier, a silanol group surface modifier, and a polymeric coating surface modifier.
48. The method of claim 38, wherein said particles have been surface modified by a silanol group surface modifier.
49. The method of claim 38, wherein said particles have been surface modified via formation of an organic covalent bond between an organic group of the particle and a surface modifier.
50. The method of claim 38 wherein said porous hybrid particles are prepared by prepolymerizing one or more organoalkoxysilanes and a tetraalkoxysilane to produce a polyorganoalkoxysiloxane, and preparing an aqueous suspension of said polyorganoalkoxysiloxane, and gelling in the presence of a base catalyst so as to produce said porous hybrid particles.
51. The method of claim 38 wherein said porous hybrid particles are prepared by prepolymerizing one or more organotrialkoxysilanes and a tetraalkoxysilane to produce a polyalkyloxysiloxane, preparing an aqueous suspension of said polyalkyloxysiloxane, and gelling in the presence of a base catalyst so as to produce said porous hybrid particles.
52. The method of claim 50 or 51 wherein said pore structure of said porous hybrid particles is modified by further including a surfactant or combination of different surfactants in said suspension, and by subjecting said porous hybrid particles to hydrothermal treatment.
53. The method of claim 50 or 51 wherein said pore structure of said porous hybrid particles is modified by further including a combination of different surfactants in said suspension, and by subjecting said porous hybrid particles to hydrothermal treatment.
54. The method of claim 52 wherein said surfactant or combination of surfactants are selected from the group consisting of Triton X-45, sodium dodecylsulfate, tris(hydroxymethyl)aminomethane lauryl sulfate, and any combination thereof.
55. The method of claim 38 wherein said method further comprises surface modifying said porous hybrid particles.
56. The method of claim 50 wherein said prepolymerization step comprises hydrolyzing and condensing a mixture of one or more organoalkoxysilanes and a tetraalkoxysilane in the presence of an acid catalyst to produce said polyalkyloxysiloxane.
57. The method of claim 51 wherein said prepolymerization step comprises hydrolyzing and condensing a mixture of one or more organotrialkoxysilanes and a tetraalkoxysilane in the presence of an acid catalyst to produce said polyalkyloxysiloxane.
58. A method of preparation of a porous inorganicorganic hybrid monolith material, comprising porous inorganicorganic hybrid particles that have a chromatographically-enhancing pore geometry, comprising the steps of
a) forming porous inorganicorganic hybrid particles,
b) modifying the pore structure of said porous hybrid particles,
c) surface modifying said porous hybrid particles, and
d) coalescing said porous hybrid particles to form a monolith material,
wherein said particles have been surface modified by a surface modifier selected from the group consisting of an organic group surface modifier, a silanol group surface modifier, a polymeric coating surface modifier, and combinations thereof.
59. The method of claim 58 wherein the surface modification step includes surface modifying said porous hybrid particles with a surface modifier having the formula Za(R)bSiR, where ZCl, Br, I, C1-C5 alkoxy, dialkylamino or trifluoromethanesulfonate; a and b are each an integer from 0 to 3 provided that ab3; R is a C1-C6 straight, cyclic or branched alkyl group, and R is a functionalizing group.
60. The method of claim 58, wherein said particles have been surface modified by a polymeric coating surface modifier.
61. The method of claim 58, wherein said particles have been surface modified by a combination of an organic group surface modifier and a silanol group surface modifier.
62. The method of claim 58, wherein said particles have been surface modified by a combination of an organic group surface modifier and a polymeric coating surface modifier.
63. The method of claim 58, wherein said particles have been surface modified by a combination of a silanol group surface modifier and a polymeric coating surface modifier.
64. The method of claim 58, wherein said particles have been surface modified by a combination of an organic group surface modifier, a silanol group surface modifier, and a polymeric coating surface modifier.
65. The method of claim 58, wherein said particles have been surface modified by a silanol group surface modifier.
66. The method of claim 58, wherein said particles have been surface modified via formation of an organic covalent bond between an organic group of the particle and a surface modifier.
67. The method of claim 58, wherein the porous hybrid particles are coalesced by sintering.
68. The method of claim 58, wherein the porous hybrid particles are mixed with a second material that is removed after coalescence of the porous hybrid particles.
69. The method of claim 68, wherein the second material is unbonded silica.
70. The method of claim 59 wherein R is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, t-butyl, sec-butyl, pentyl, isopentyl, hexyl and cyclohexyl.
71. The method of claim 59 wherein said functionalizing group R is a C1-C30 alkyl group.
72. The method of claim 59 wherein said functionalizing group R is a C1-C20 alkyl group.
73. The method of claim 59 wherein said surface modifier is selected from the group consisting of octyltrichlorosilane, octadecyltrichlorosilane, octyldimethylchlorosilane, and octadecyldimethylchlorosilane.
74. The method of claim 73 wherein said surface modifier is selected from the group consisting of octyltrichlorosilane and octadecyltrichlorosilane.
75. The method of claim 59, wherein said 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, or an alkyl or aryl group containing an embedded polar functionality.
76. The method of claim 55 wherein any free silanol groups remaining from said surface modification procedure are endcapped.
77. The method of claim 50 wherein the molar ratio of said organoalkoxysilane and tetraalkoxysilane is from about 0.5:1 to 0.2:1.
78. The method of claim 50 wherein the molar ratio of said organotrialkoxysilane and tetraalkoxysilane is from about 0.5:1 to 0.2:1.
79. The method of claim 38 wherein said porous hybrid particles have a specific surface area of about 50 to 800 m2g.
80. The method of claim 38 wherein said porous hybrid particles have a specific surface area of about 100 to 350 m2g.
81. The method of claim 38 wherein said porous hybrid particles have specific pore volumes of about 0.25 to 1.5 cm3g.
82. The method of claim 38 wherein said porous hybrid particles have specific pore volumes of about 0.4 to 1.2 cm3g.
83. The method of claim 38 wherein said porous hybrid particles have an average pore diameter of about 50 to 500 .
84. The method of claim 38 wherein said porous hybrid particles have a micropore surface area of less than about 110 m2g.
85. The method of claim 38 wherein said porous hybrid particles have an average pore diameter of about 100 to 300 .
86. The method of claim 38, wherein said porous hybrid particles have a specific surface area of about 50 to 800 m2g, said porous hybrid particles have specific pore volumes of about 0.25 to 1.5 cm3g, and said porous hybrid particles have an average pore diameter of about 50 to 500 .
87. The method of claim 50 wherein said suspension further comprises a porogen.
88. The method of claim 87 wherein said porogen is toluene.
89. The method of claim 50 wherein said tetraalkoxysilane has the formula Si(OR1)4, where R1 is a C1-C3 alkyl moiety.
90. The method of claim 50 wherein said tetraalkoxysilane is selected from the group consisting of tetramethoxysilane and tetraethoxysilane.
91. The method of claim 50 wherein said organoalkoxysilane has the formula R2Si(OR1)3 or R6Si(OR1)3m where R2 is a C1-C18 aliphatic, styryl, vinyl, propanol or aromatic moiety, R1 is a C1-C4 alkyl moiety, R6 is a C1-C18 alkylene, alkenylene, alkynylene or arylene moiety bridging two or more silicon atoms, and m is an integer greater than or equal to two.
92. The method of claim 50 wherein said organotrialkoxysilane has the formula R2Si(OR1)3, where R2 is a C1-C18 aliphatic or aromatic moiety and R1 is a C1-C4 alkyl moiety.
93. The method of claim 50 wherein said base catalyst is free of alkali or alkaline earth metal cations.
94. The method of claim 93 wherein said base catalyst is ammonium hydroxide.
95. The method of claim 91 wherein R2 is methyl, ethyl, phenyl, vinyl, methacryloxypropyl, or styrylethyl and R1 is ethyl; or R6 is a bridging ethylene group, m2, and R1 is ethyl or methyl.
96. The method of claim 38 wherein said porous inorganicorganic hybrid particles have the formula SiO2(R2pR4qSiOt)n or SiO2R6(R2rSiOt)mn wherein R2 and R4 are independently C1-C18 aliphatic, styryl, vinyl, propanol, or aromatic moieties, R6is a substituted or unsubstituted C1-C18 alkylene, alkenylene, alkynylene or arylene moiety bridging two or more silicon atoms, p and q are 0, 1 or 2, provided that pq1 or 2, and that when pq1, t1.5, and when pq2, t1; r is 0 or 1, provided that when r0, t1.5, and when r1, t1; m is an integer greater than or equal to 2, and n is a number from 0.03 to 1.
97. The method of claim 96, wherein n is a number from 0.1 to 1
98. The method of claim 96 wherein said porous inorganicorganic hybrid particles have average pore diameters of about 100 to 300 .
99. The method of claim 96 wherein n is a number from 0.2 to 0.5.
100. A separations device comprising a porous inorganicorganic hybrid monolith material having a chromatographically-enhancing pore geometry.
101. The separations device of claim 100, wherein the monolith material further comprises coalesced porous inorganicorganic hybrid particles having a chromatographically-enhancing pore geometry.
102. The separations device of claim 100, wherein said porous hybrid monolith material has a specific surface area of about 100 to 350 m2g.
103. The separations device of claim 100 wherein said porous hybrid monolith material has a micropore surface area of less than about 110 m2g.
104. The separations device of claim 101, wherein said porous hybrid monolith material has a specific pore volumes of about 0.4 to 1.2 cm3g.
105. The separations device of claim 101, wherein said porous hybrid monolith material has a micropore surface area of less than about 105 m2g.
106. The separations device of claim 101, wherein said porous hybrid monolith material has a micropore surface area of less than about 80 m2g.
107. The separations device of claim 101, said porous hybrid monolith material has a micropore surface area of less than about 50 m2g.
108. The separations device of claim 101, wherein said porous hybrid monolith material has average pore diameter of about 100 to 300 .
109. The separations device of claim 100 or 101, wherein said device is selected from the group consisting of chromatographic columns, thin layer plates, filtration membranes, sample cleanup devices, and microtiter plates.
110. The separations device of claim 101, wherein said porous hybrid particles have a specific surface area of about 100 to 350 m2g.
111. The separations device of claim 101 wherein said porous hybrid particles have a micropore surface area of less than about 110 m2g.
112. The separations device of claim 101, wherein said porous hybrid particles have specific pore volumes of about 0.4 to 1.2 cm3g.
113. The separations device of claim 101, wherein said porous hybrid particles have a micropore surface area of less than about 105 m2g.
114. The separations device of claim 101, wherein said porous hybrid particles have a micropore surface area of less than about 80 m2g.
115. The separations device of claim 101, said porous hybrid particles have a micropore surface area of less than about 50 m2g.
116. The separations device of claim 101, wherein said porous hybrid particles have an average pore diameter of about 100 to 300 .
117. A separations device comprising a porous inorganicorganic hybrid monolith material, wherein said monolith material is comprised of coalesced porous inorganicorganic hybrid particles, and wherein said particles have been surface modified by a surface modifier selected from the group consisting of an organic group surface modifier, a silanol group surface modifier, a polymeric coating surface modifier, and combinations thereof.
118. The separations device of claim 117, wherein the porous hybrid particles have a chromatographically-enhancing pore geometry and have been surface modified with a surface modifier having the formula Za(R)bSiR, where ZCl, Br, I, C1-C5 alkoxy, dialkylamino or trifluoromethanesulfonate; a and b are each an integer from 0 to 3 provided that ab3; R is a C1-C6 straight, cyclic or branched alkyl group and R is a functionalizing group.
119. The separations device of claim 118, wherein said surface modifier is selected from the group consisting of octyltrichlorosilane, octadecyltrichlorosilane, octyldimethylchlorosilane, and octadecyldimethylchlorosilane.
120. The separations device of claim 119, wherein said surface modifier is selected from the group consisting of octyltrichlorosilane and octadecyltrichlorosilane.
121. The separations device of claim 118, wherein said 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, or an alkyl or aryl group containing an embedded polar functionality.
122. The separations device of claim 118, wherein said functionalizing group R is a C1-C30 alkyl group.
123. The separations device of claim 118, wherein said functionalizing group R is a C1-C20 alkyl group.
124. The separations device of claim 101, wherein said porous hybrid particles have the formula SiO2(R2pR4qSiOt)n or SiO2R6(R2rSiOt)mn wherein R2 and R4 are independently C1-C18 aliphatic, styryl, vinyl, propanol, or aromatic moieties, R6is a substituted or unsubstituted C1-C18 alkylene, alkenylene, alkynylene or arylene moiety bridging two or more silicon atoms, p and q are 0, 1 or 2, provided that pq1 or 2, and that when pq1, t1.5, and when pq2, t1; r is 0 or 1, provided that when r0, t1.5, and when r1, t1; m is an integer greater than or equal to 2, and n is a number from 0.03 to 1.
125. The separations device of claim 124, wherein n is a number from 0.1 to 1.
126. The separations device of claim 124, wherein said porous hybrid particles have average pore diameters of about 100 to 300 .
127. The separation device of claim 124 wherein n is a number from 0.2 to 0.5.
128. The separations device of claim 101 wherein said inorganic portion of said hybrid monolith material is selected from the group consisting of alumina, silica, titanium or zirconium oxides, and ceramic materials.
129. The separations device of claim 101 wherein said inorganic portion of said hybrid monolith material is silica.
130. A chromatographic column having improved lifetime, comprising
a) a column having a cylindrical interior for accepting a monolith material of porous inorganicorganic hybrid material, and
b) a chromatographic bed comprising a porous inorganicorganic hybrid monolith material having a chromatographically-enhancing pore geometry of the formula SiO2(R2pR4qSiOt)n or SiO2R6(R2rSiOt)mn wherein R2 and R4 are independently C1-C18 aliphatic, styryl, vinyl, propanol, or aromatic moieties, R6is a substituted or unsubstituted C1-C18 alkylene, alkenylene, alkynylene or arylene moiety bridging two or more silicon atoms, p and q are 0, 1 or 2, provided that pq1 or 2, and that when pq1, t1.5, and when pq2, t1; r is 0 or 1, provided that when r0, t1.5, and when r1, t1; m is an integer greater than or equal to 2, and n is a number from 0.03 to 1.
131. A chromatographic column having improved lifetime, comprising
a) a column having a cylindrical interior for accepting a monolith material of porous inorganicorganic hybrid material, and
b) a chromatographic bed comprising a porous inorganicorganic hybrid monolith material having a chromatographically-enhancing pore geometry, wherein said monolith material has been surface modified by a surface modifier selected from the group consisting of an organic group surface modifier, a silanol group surface modifier, a polymeric coating surface modifier, and combinations thereof.
132. The chromatographic column of claim 131 that has been surface modified with a surface modifier having the formula Za(R)bSiR, where ZCl, Br, I, C1-C5 alkoxy, dialkylamino or trifluoromethanesulfonate; a and b are each an integer from 0 to 3 provided that ab3; R is a C1-C6 straight, cyclic or branched alkyl group, and R is a functionalizing group.
133. The chromatographic column of claim 130 or 131, wherein the porous inorganicorganic hybrid monolith material is prepared from coalesced porous hybrid particles, wherein the porous hybrid particles have a chromatography-enhancing pore geometry and average pore diameters of about 100 to 300 , and said porous hybrid particles of hybrid silica have been surface modified
134. The chromatographic column of claim 130, wherein n is a number from 0.1 to 1.
135. A method of preparation of a porous inorganicorganic hybrid monolith material, comprising coalesced porous particles of hybrid silica having a chromatography-enhancing pore geometry, comprising the steps of
a) prepolymerizing a mixture of one or more organoalkoxysilanes and a tetraalkoxysilane in the presence of an acid catalyst to produce a polyorganoalkoxysiloxane;
b) preparing an aqueous suspension of said polyorganoalkoxysiloxane, said suspension further comprising a surfactant or combination of surfactants, and gelling in the presence of a base catalyst so as to produce porous hybrid particles;
c) modifying the pore structure of said porous hybrid particles by hydrothermal treatment; and
d) coalescing said porous hybrid particles to form a monolith material thereby preparing a porous inorganicorganic hybrid monolith material.
136. The method of claim 135 wherein the molar ratio of said organotrialkoxysilane and tetraalkoxysilane is from about 0.5:1 to 0.2:1.
137. The method of claim 135 wherein said porous hybrid particles have a specific surface area of about 75 to 600 m2g.
138. The method of claim 135 wherein said porous hybrid particles have a specific surface area of about 100 to 350 m2g.
139. The method of claim 135 wherein said porous hybrid particles have a micropore surface area of less than about 110 m2g.
140. The method of claim 135 wherein said porous hybrid particles have specific pore volumes of about 0.4 to 1.2 cm3g.
141. The method of claim 135, wherein said porous hybrid particles have a micropore surface area of less than about 105 m2g.
142. The method of claim 135, wherein said porous hybrid particles have a micropore surface area of less than about 80 m2g.
143. The method of claim 135, wherein said porous hybrid particles have a micropore surface area of less than about 50 m2g.
144. The method of claim 135 wherein said porous hybrid particles have an average pore diameter of about 50 to 500 .
145. The method of claim 135 wherein said porous hybrid particles have an average pore diameter of about 100 to 300 .
146. The method of claim 135 wherein said surfactant is an alkylphenoxypolyethoxyethanol.
147. The method of claim 135 wherein said suspension further comprises a porogen.
148. The method of claim 135 wherein said tetraalkoxysilane is selected from the group consisting of tetramethoxysilane and tetraethoxysilane.
149. The method of claim 135, wherein said porous hybrid particles have the formula SiO2(R2pR4qSiOt)n or SiO2R (R2rSiOt)mn wherein R2 and R4 are independently C1-C18 aliphatic, styryl, vinyl, propanol, or aromatic moieties, R6is a substituted or unsubstituted C1-C18 alkylene, alkenylene, alkynylene or arylene moiety bridging two or more silicon atoms, p and q are 0, 1 or 2, provided that pq1 or 2, and that when pq1, t1.5, and when pq2, t1; r is 0 or 1, provided that when r0, t1.5, and when r1, t1; m is an integer greater than or equal to 2, and n is a number from 0.03 to 1.
150. The method of claim 135, wherein n is a number from 0.1 to 1.
151. The method of claim 149, wherein said porous hybrid particles have average pore diameters of about 100 to 300 .
152. The method of claim 149 wherein n is a number from 0.2 to 0.5.
153. A porous inorganicorganic hybrid monolith material comprising coalesced porous hybrid particles of hybrid silica having a chromatographically-enhancing pore geometry, produced by the process of
a) prepolymerizing a mixture of one or more organoalkoxysilanes and a tetraalkoxysilane in the presence of an acid catalyst to produce a polyorganoalkoxysiloxane;
b) preparing an aqueous suspension of said polyorganoalkoxysiloxane, said suspension further comprising a surfactant or a combination of surfactants, and gelling in the presence of a base catalyst so as to produce porous hybrid particles;
c) modifying the pore structure of said porous hybrid particles by hydrothermal treatment; and
d) coalescing said porous hybrid particles to form a monolith material.
154. The hybrid monolith material of claim 153 wherein the molar ratio of said organoalkoxysilane and tetraalkoxysilane is from about 0.5:1 to 0.2:1.
155. The hybrid monolith material of claim 153 wherein said porous hybrid particles have a specific surface area of about 75 to 600 m2g.
156. The hybrid monolith material of claim 153 wherein said porous hybrid particles have a specific surface area of about 100 to 350 m2g.
157. The hybrid monolith material of claim 153 wherein said porous hybrid particles have specific pore volumes of about 0.4 to 1.2 cm3g.
158. The hybrid monolith material of claim 153 wherein said porous hybrid particles have a micropore surface area of less than about 110 m2g.
159. The hybrid monolith material of claim 153, wherein said porous hybrid particles have a micropore surface area of less than about 105 m2g.
160. The hybrid monolith material of claim 153, wherein said porous hybrid particles have a micropore surface area of less than about 80 m2g.
161. The hybrid monolith material of claim 153, wherein said porous hybrid particles have a micropore surface area of less than about 50 m2g.
162. The hybrid monolith material of claim 153 wherein said porous hybrid particles have an average pore diameter of about 50 to 500 .
163. The hybrid monolith material of claim 153 wherein said porous hybrid particles have an average pore diameter of about 100 to 300 .
164. The hybrid monolith material of claim 153 wherein said surfactant is an alkylphenoxypolyethoxyethanol.
165. The hybrid monolith material of claim 153 wherein said suspension further comprises a porogen.
166. The hybrid monolith material of claim 153 wherein said tetraalkoxysilane is selected from the group consisting of tetramethoxysilane and tetraethoxysilane.
167. The hybrid monolith material of claim 153, having the formula SiO2(R2pR4qSiOt)n or SiO2R6(R2rSiOt)mn wherein R2 and R4 are independently C1-C18 aliphatic, styryl, vinyl, propanol, or aromatic moieties, R6is a substituted or unsubstituted C1-C18 alkylene, alkenylene, alkynylene or arylene moiety bridging two or more silicon atoms, p and q are 0, 1 or 2, provided that pq1 or 2, and that when pq1, t1.5, and when pq2, t1; r is 0 or 1, provided that when r0, t1.5, and when r1, t1; m is an integer greater than or equal to 2, and n is a number from 0.03 to 1.
168. The hybrid monolith material of claim 167, wherein said porous hybrid particles have average pore diameters of about 100 to 300 .
169. The hybrid monolith material of claim 167 wherein n is a number from 0.20 to 0.5.
170. The hybrid monolith material of claim 167, wherein n is a number from 0.1 to 1.
171. A porous inorganicorganic hybrid monolith material having a chromatographically-enhancing pore geometry, wherein said material contains a plurality of macropores sufficient to result in reduced backpressure at chromatographically-useful flow rates.
172. The hybrid monolith material of claim 171, wherein the macropores are pores with a pore diameter larger than about 0.05 m.
173. A porous inorganicorganic hybrid monolith material, having a chromatographically-enhancing pore geometry, wherein said monolith material has been surface modified by a surface modifier selected from the group consisting of an organic group surface modifier, a silanol group surface modifier, a polymeric coating surface modifier, and combinations thereof.
174. The hybrid monolith material of claim 173, wherein said monolith material has been surface modified with a surface modifier having the formula Za(R)bSiR, where ZCl, Br, I, C1-C5 alkoxy, dialkylamino or trifluoromethanesulfonate; a and b are each an integer from 0 to 3 provided that ab3; R is a C1-C6 straight, cyclic or branched alkyl group, and R is a functionalizing group.
175. The hybrid monolith material of claim 172 or 174, wherein said monolith has been surface modified by a polymeric coating surface modifier.
176. The hybrid monolith material of claim 174 wherein R is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, t-butyl, sec-butyl, pentyl, isopentyl, hexyl and cyclohexyl.
177. The hybrid monolith material of claim 174, 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, or an alkyl or aryl group containing an embedded polar functionality.
178. The hybrid monolith material of claim 177, wherein said functionalizing group R is a C1-C30 alkyl group.
179. The hybrid monolith material of claim 177, wherein said functionalizing group R is a C1-C20 alkyl group.
180. The hybrid monolith material of claim 174, wherein said surface modifier is selected from the group consisting of octyltrichlorosilane, octadecyltrichlorosilane, octyldimethylchlorosilane, octadecyldimethylchlorosilane, and octadecyltrimethoxysilane.
181. The hybrid monolith material of claim 180, wherein said surface modifier is selected from the group consisting of octyltrichlorosilane and octadecyltrichlorosilane.
182. The hybrid monolith material of claim 180, wherein said surface modifier is octadecyltrichlorosilane.
183. The hybrid monolith material of claim 171 or 173 having the formula SiO2(R2pR4qSiOt)n or SiO2R6(R2rSiOt)mn wherein R2 and R4 are independently C1-C18 aliphatic, styryl, vinyl, propanol, or aromatic moieties, R6 is a substituted or unsubstituted C1-C18 alkylene, alkenylene, alkynylene or arylene moiety bridging two or more silicon atoms, p and q are 0, 1 or 2, provided that pq1 or 2, and that when pq1, t1.5, and when pq2, t1; r is 0 or 1, provided that when r0, t1.5, and when r1, t1; m is an integer greater than or equal to 2, and n is a number from 0.03 to 1.
184. The hybrid monolith material of claim 183, wherein n is a number from 0.1 to 1
185. The hybrid monolith material of claim 183 wherein n is a number from 0.2 to 0.5.
186. The hybrid monolith material of claim 171 or 173 wherein said inorganic portion of said hybrid monolith material is selected from the group consisting of alumina, silica, titanium or zirconium oxides, and ceramic materials.
187. The hybrid monolith material of claim 171 or 173 wherein said inorganic portion of said hybrid monolith material is silica.
188. The hybrid monolith material of claim 171 or 174, wherein said monolith material has been surface modified by a combination of an organic group surface modifier and a silanol group surface modifier.
189. The hybrid monolith material of claim 171 or 174, wherein said monolith material has been surface modified by a combination of an organic group surface modifier and a polymeric coating surface modifier.
190. The hybrid monolith material of claim 171 or 174, wherein said monolith material has been surface modified by a combination of a silanol group surface modifier and a polymeric coating surface modifier.
191. The hybrid monolith material of claim 171 or 174, wherein said monolith material has been surface modified by a combination of an organic group surface modifier, a silanol group surface modifier, and a polymeric coating surface modifier.
192. The hybrid monolith material of claim 171 or 174, wherein said monolith material has been surface modified by a silanol group surface modifier.
193. The hybrid monolith material of claim 171 or 174, wherein said monolith material has been surface modified via formation of an organic covalent bond between an organic group of the particle and a surface modifier.
194. A method of preparation of a porous inorganicorganic hybrid monolith material having a chromatographically-enhancing pore geometry, comprising the steps of
a) forming a porous inorganicorganic monolith material and
b) modifying the pore structure of said porous monolith material.
195. The method of claim 194, wherein said monolith material has been surface modified by a surface modifier selected from the group consisting of an organic group surface modifier, a silanol group surface modifier, a polymeric coating surface modifier, and combinations thereof.
196. The method of claim 195, wherein said monolith has been surface modified by a polymeric coating surface modifier.
197. The method of claim 195, wherein said monolith material has been surface modified by a combination of an organic group surface modifier and a silanol group surface modifier.
198. The method of claim 195, wherein said monolith material has been surface modified by a combination of an organic group surface modifier and a polymeric coating surface modifier.
199. The method of claim 195, wherein said monolith material has been surface modified by a combination of a silanol group surface modifier and a polymeric coating surface modifier.
200. The method of claim 195, wherein said monolith material has been surface modified by a combination of an organic group surface modifier, a silanol group surface modifier, and a polymeric coating surface modifier.
201. The method of claim 195, wherein said monolith material has been surface modified by a silanol group surface modifier.
202. The method of claim 195, wherein said monolith material has been surface modified via formation of an organic covalent bond between an organic group of the particle and a surface modifier.
203. The method of claim 194 wherein said monolith material is prepared by
a) preparing an aqueous solution of a mixture of one or more organoalkoxysilanes and a tetraalkoxysilane in the presence of an acid catalyst, and a surfactant or combination of surfactants to produce a polyorganoalkoxysiloxane;
b) incubating said solution, resulting in a three-dimensional gel having a continuous, interconnected pore structure,
c) aging the gel at a controlled pH and temperature to yield a solid monolith material, and
d) rinsing the monolith material with an aqueous basic solution at an elevated temperature.
204. The method of claim 194 wherein said monolith material are prepared by
a) preparing an aqueous solution of a mixture of one or more organotrialkoxysilanes and a tetraalkoxysilane in the presence of an acid catalyst, and a surfactant or combination of surfactants to produce a polyorganoalkoxysiloxane;
b) incubating said solution, resulting in a three-dimensional gel having a continuous, interconnected pore structure,
c) aging the gel at a controlled pH and temperature to yield a solid monolith material, and
d) rinsing the monolith material with an aqueous basic solution at an elevated temperature.
205. The method of claim 203 or 204, wherein said surfactant or combination of surfactants are selected from the group consisting of Pluronic P-105, Pluronic P-123, Triton 405, and Triton X-100, and any combination thereof.
206. The method of claim 203 wherein said pore structure of said monolith material is modified by hydrothermal treatment further, rinsed with water followed by a solvent exchange, dried at room temperature, and dried at elevated temperature under vacuum.
207. The method of claim 194 wherein said method further comprises surface modifying said porous monolith materials.
208. A method of preparation of a porous inorganicorganic hybrid monolith material having a chromatographically-enhancing pore geometry, comprising the steps of
a) forming a porous inorganicorganic monolith material,
b) modifying the pore structure of said porous monolith material, and
c) modifying the surface of said porous monolith material,
wherein said monolith material has been surface modified by a surface modifier selected from the group consisting of an organic group surface modifier, a silanol group surface modifier, a polymeric coating surface modifier, and combinations thereof.
209. The method of claim 208, wherein the surface modification step includes surface modifying said porous monolith material with a surface modifier having the formula Za(R)bSiR, where ZCl, Br, I, C1-C5 alkoxy, dialkylamino or trifluoromethanesulfonate; a and b are each an integer from 0 to 3 provided that ab3; R is a C1-C6 straight, cyclic or branched alkyl group, and R is a functionalizing group.
210. The method of claim 209, wherein said monolith has been surface modified by a polymeric coating surface modifier.
211. The method of claim 209, wherein said monolith material has been surface modified by a combination of an organic group surface modifier and a silanol group surface modifier.
212. The method of claim 209, wherein said monolith material has been surface modified by a combination of an organic group surface modifier and a polymeric coating surface modifier.
213. The method of claim 209, wherein said monolith material has been surface modified by a combination of a silanol group surface modifier and a polymeric coating surface modifier.
214. The method of claim 209, wherein said monolith material has been surface modified by a combination of an organic group surface modifier, a silanol group surface modifier, and a polymeric coating surface modifier.
215. The method of claim 209, wherein said monolith material has been surface modified by a silanol group surface modifier.
216. The method of claim 209, wherein said monolith material has been surface modified via formation of an organic covalent bond between an organic group of the particle and a surface modifier.
217. The method of claim 209 wherein R is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, t-butyl, sec-butyl, pentyl, isopentyl, hexyl and cyclohexyl.
218. The method of claim 209 wherein said functionalizing group R is a C1-C30 alkyl group.
219. The method of claim 209 wherein said functionalizing group R is a C1-C20 alkyl group.
220. The method of claim 209 wherein said surface modifier is selected from the group consisting of octyltrichlorosilane, octadecyltrichlorosilane, octyldimethylchlorosilane, octadecyldimethylchlorosilane, and octadecyltrimethoxysilane.
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 220 wherein said surface modifier is octadecyltrichlorosilane.
223. The method of claim 209, wherein said 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, or an alkyl or aryl group containing an embedded polar functionality.
224. The method of claim 207 wherein any free silanol groups remaining from said surface modification procedure are endcapped.
225. The method of claim 203 wherein the molar ratio of said organoalkoxysilane and tetraalkoxysilane is from about 0.5:1 to 0.2:1.
226. The method of claim 204 wherein the molar ratio of said organotrialkoxysilane and tetraalkoxysilane is from about 0.5:1 to 0.2:1.
227. The method of claim 203 or 204 wherein said tetraalkoxysilane has the formula Si(OR1)4, where R1 is a C1-C3 alkyl moiety.
228. The method of claim 203 or 204 wherein said tetraalkoxysilane is selected from the group consisting of tetramethoxysilane and tetraethoxysilane.
229. The method of claim 203 wherein said organoalkoxysilane has the formula R2Si(OR1)3 or R6Si(OR1)3m where R2 is a C1-C18 aliphatic, styryl, vinyl, propanol, or aromatic moiety, R1 is a C1-C4 alkyl moiety, R6 is a C1-C18 alkylene, alkenylene, alkynylene or arylene moiety bridging two or more silicon atoms, and m is an integer greater than or equal to two.
230. The method of claim 204 wherein said organotrialkoxysilane has the formula R2Si(OR1)3, where R2 is a C1-C18 aliphatic or aromatic moiety and R1 is a C1-C4 alkyl moiety.
231. The method of claim 203 or 204 wherein said aqueous basic solution is ammonium hydroxide.
232. The method of claim 229 wherein R2 is methyl, ethyl, phenyl, vinyl, methacryloxypropyl, or styrylethyl and R1 is ethyl; or R6 is a bridging ethylene group, m2, and R1 is ethyl.
233. The method of claim 194 wherein said porous inorganicorganic hybrid monolith material has the formula SiO2(R2pR4qSiOt)n or SiO2R6(R2rSiOt)mn wherein R2 and R4 are independently C1-C18 aliphatic, styryl, vinyl, propanol, or aromatic moieties, R6is a substituted or unsubstituted C1-C18 alkylene, alkenylene, alkynylene or arylene moiety bridging two or more silicon atoms, p and q are 0, 1 or 2, provided that pq1 or 2, and that when pq1, t1.5, and when pq2, t1; r is 0 or 1, provided that when r0, t1.5, and when r1, t1; m is an integer greater than or equal to 2, and n is a number from 0.03 to 1.
234. The method of claim 233, wherein n is a number from 0.1 to 1
235. The method of claim 233 wherein n is a number from 0.20 to 0.5.
236. A separations device comprising a porous inorganicorganic hybrid monolith material having a chromatographically-enhancing pore geometry, wherein said monolith material has been surface modified by a surface modifier selected from the group consisting of an organic group surface modifier, a silanol group surface modifier, a polymeric coating surface modifier, and combinations thereof.
237. The method of claim 236, wherein said monolith material has been surface modified with a surface modifier having the formula Za(R)bSiR, where ZCl, Br, I, C1-C5 alkoxy, dialkylamino or trifluoromethanesulfonate; a and b are each an integer from 0 to 3 provided that ab3; R is a C1-C6 straight, cyclic or branched alkyl group, and R is a functionalizing group.
238. A method of preparation of a porous inorganicorganic hybrid monolith material having a chromatographically-enhancing pore geometry comprising
a) preparing an aqueous solution of a mixture of one or more organoalkoxysilanes and a tetraalkoxysilane in the presence of an acid catalyst, and a surfactant or combination of surfactants to produce a polyorganoalkoxysiloxane;
b) incubating said solution, resulting in a three-dimensional gel having a continuous, interconnected pore structure,
c) aging the gel at a controlled pH and temperature to yield a solid monolith material,
d) rinsing the monolith material with an aqueous basic solution at an elevated temperature,
e) modifying the pore structure of said monolith material by hydrothermal treatment,
f) rinsing the monolith material with water followed by a solvent exchange, and
g) drying the monolith material at room temperature drying and at an elevated temperature under vacuum.
thereby preparing a porous inorganicorganic hybrid monolith material.
239. The method of claim 238, wherein the solvent is exchanged to methanol
240. A porous inorganicorganic hybrid monolith material having a chromatographically-enhancing pore geometry, produced by the process of
a) preparing an aqueous solution of a mixture of one or more organotrialkoxysilanes and a tetraalkoxysilane in the presence of an acid catalyst, and a surfactant or combination of surfactants to produce a polyorganoalkoxysiloxane;
b) incubating said solution, resulting in a three-dimensional gel having a continuous, interconnected pore structure,
c) aging the gel at a controlled pH and temperature to yield a solid monolith material, and
d) rinsing the monolith material with an aqueous basic solution at an elevated temperature
e) modifying the pore structure of said monolith material by hydrothermal treatment,
f) rinsing the monolith material with water followed by a solvent exchange, and
g) drying the monolith material at room temperature drying and at an elevated temperature under vacuum.
241. The hybrid monolith material of claim 240, wherein the solvent is exchanged to methanol, ethanol, acetonitrile, tetrahydrofuran, or hexane and the elevated temperature is about 70 to 120 C.
242. The hybrid monolith material of claim 241, wherein the solvent is exchanged to methanol and the elevated temperature is about 100 C.
243. The hybrid monolith material of claim 238, wherein the organoalkoxysilane is methyltrimethoxysilane and the tetraalkoxysilane is tetramethoxysilane.
244. The hybrid monolith material of claim 238, wherein the organoalkoxysilane is 1,2-bis-(trimethoxysilyl)ethane and the tetraalkoxysilane is tetramethoxysilane.
245. The hybrid monolith material of claim 238, wherein the organoalkoxysilane is methacryloxypropyltrimethoxysilane and the tetraalkoxysilane is tetramethoxysilane.
246. The hybrid monolith material of claim 238, wherein the acid catalyst is a solution of acetic acid.
247. The hybrid monolith material of claim 238, wherein the acid catalyst is an aqueous solution of acetic acid.
248. The hybrid monolith material of claim 238, wherein the acetic acid is about 0.1 mM to 500 mM.
249. The hybrid monolith material of claim 246, wherein the acetic acid is about 10 mM to 150 mM.
250. The hybrid monolith material of claim 246, wherein the acetic acid is about 50 mM to 120 mM.
251. The hybrid monolith material of claim 238, wherein the surfactant is Pluronic P-105.
252. The hybrid monolith material of claim 238, wherein the surfactant is Pluronic P-123.
253. The hybrid monolith material of claim 238, wherein the surfactant is Triton X-100.
254. The hybrid monolith material of claim 238, wherein the surfactant is Triton 405.
255. The hybrid monolith material of claim 238, wherein the surfactant concentration is about 3% and 15% by weight.
256. The hybrid monolith material of claim 238, wherein the surfactant concentration is about 7% to 12% by weight.
257. The hybrid monolith material of claim 238, wherein the surfactant concentration is about 8% to 10% by weight.
258. The hybrid monolith material of claim 238, wherein the total concentration of organoalkoxysilane and tetraalkoxysilane is about <5 gml.
259. The hybrid monolith material of claim 238, wherein the total concentration of organoalkoxysilane and tetraalkoxysilane is about <2 gml.
260. The hybrid monolith material of claim 238, wherein the total concentration of organoalkoxysilane and tetraalkoxysilane is about <1 gml.
261. The hybrid monolith material of claim 238, wherein the incubation temperature is about 90 C. to the point at which the solution physically freezes.
262. The hybrid monolith material of claim 238, wherein the incubation temperature is about 20 C. to 70 C.
263. The hybrid monolith material of claim 238, wherein the incubation temperature is about 35 C. to 60 C.
264. The hybrid monolith material of claim 238, wherein gel is aged from about 5 hours to 10 days.
265. The hybrid monolith material of claim 238, wherein gel is aged from about 10 hours to 7 days.
266. The hybrid monolith material of claim 238, wherein gel is aged from about 2 days to 5 days.
267. The hybrid monolith material of claim 238, wherein gel is aged at pH of about 2-3.
268. The hybrid monolith material of claim 238, wherein gel is aged at about 20 C. to 70 C.
269. The hybrid monolith material of claim 238, wherein gel is aged at about 35 C. to 60 C.
270. The hybrid monolith material of claim 238, wherein the aqueous basic solution is ammonium hydroxide.
271. The hybrid monolith material of claim 238, wherein the concentration of aqueous basic solution is from about 105 N to 1 N.
272. The hybrid monolith material of claim 238, wherein the concentration of aqueous basic solution is from about 104 N to 0.5 N.
273. The hybrid monolith material of claim 238, wherein the concentration of aqueous basic solution is from about 103 N to 0.1 N.
274. The hybrid monolith material of claim 238, wherein the elevated temperature of rinsing is from about 0 C. to 80 C.
275. The hybrid monolith material of claim 238, wherein the elevated temperature of rinsing is from about 20 C. to 70 C.
276. The hybrid monolith material of claim 238, wherein the elevated temperature of rinsing is from about 40 C. to 60 C.
277. The hybrid monolith material of claim 238, wherein the rinsing time is from about 1 to 6 days.
278. The hybrid monolith material of claim 238, wherein the rinsing time is from about 1.5 to 4.5 days.
279. The hybrid monolith material of claim 238, wherein the rinsing time is from about 2 to 3 days.
280. The hybrid monolith material of claim 238, wherein the hydrothermal treatment is at pH is from about 7.0 to 12.0.
281. The hybrid monolith material of claim 238, wherein the hydrothermal treatment is at pH from about 7.3 to 11.0.
282. The hybrid monolith material of claim 238, wherein the hydrothermal treatment is at pH from about 7.5 to 10.6.
283. The hybrid monolith material of claim 238, wherein the hydrothermal treatment is at 110 C. to 180 C.
284. The hybrid monolith material of claim 238, wherein the hydrothermal treatment is at 120 C. to 160 C.
285. The hybrid monolith material of claim 238, wherein the hydrothermal treatment is at 130 C. to 155 C.
286. A porous inorganicorganic hybrid monolith material, comprising coalesced porous inorganicorganic hybrid particles having a chromatographically-enhancing pore geometry and a formula SiO2C2H4(SiO1 5)20 25 wherein said hybrid particles have been surface modified with octadecyltrichlorosilane and wherein any free silanol groups remaining from said surface modification are endcapped with chlorotrimethylsilane.
287. A porous inorganicorganic hybrid monolith material comprising coalesced porous hybrid particles of hybrid silica having a chromatographically-enhancing pore geometry and a formula SiO2C2H4(SiO1 5)20 25 produced by the process of
a) prepolymerizing a 0.251.0 mole ratio mixture of bis(triethoxysilyl)ethane and tetraethoxysilane in the presence of 0.1 molar hydrochloric acid to produce a polyorganosiloxane;
b) preparing an aqueous suspension of said polyorganoalkoxysiloxane, said suspension further comprising the surfactant Triton X-100, and gelling said suspension in the presence of a ammonium hydroxide so as to produce porous hybrid parties;
c) modifying the pore structure of said porous hybrid particles by hydrothermal treatment at 155 C. for 20 h in 0.3 M tris(hydroxymethyl)aminomethane, pH adjusted to 9.80;
d) sizing to a nominal 2 m particle diameter;
e) acid washing in a 1 molar hydrochloric acid solution;
f) further surface modifying with octadecyltrichlorosilane wherein any free silanol groups remaining from said surface modification are endcapped with chlorotrimethylsilane; and
g) coalescing said porous hybrid particles to form a monolith material.
288. A porous inorganicorganic hybrid monolith material having a chromatographically-enhancing pore geometry and a formula SiO2CH3SiO1.50.5 wherein said hybrid material has been surface modified with octadecyltrichlorosilane and wherein any free silanol groups remaining from said surface modification procedure are endcapped with chlorotrimethylsilane and wherein said material contains a plurality of macropores sufficient to result in reduced backpressure at chromatographically-useful flow rates.
289. A porous inorganicorganic hybrid monolith material having a chromatographically-enhancing pore geometry and a formula SiO2CH3SiO1 50 5, produced by the process of
a) preparing an aqueous solution of methyltrimethoxysilane and a tetramethoxysilane in the presence of a 0.07 molar acetic acid solution and the surfactant Pluronic P-105 or Trition X-100 to produce a polyorganoalkoxysiloxane;
a) incubating said solution for 3 days at 45 C., resulting in a three-dimensional gel having a continuous, interconnected pore structure;
b) aging the gel in 1 molar ammonium hydroxide at 60 C. for 3 days to yield a solid monolith material;
c) rinsing the monolith material with water;
d) modifying the pore structure of said monolith material by hydrothermal treatment at155 C. for 20 h in 0.1 molar tris(hydroxymethyl)aminomethane, pH adjusted to 8.0;
e) rinsing the monolith material with water followed by a solvent exchange;
f) acid washing the monolith material in 1 molar hydrochloric acid for 24 hours at 98 C.;
g) rinsing the monolith material with water followed by a solvent exchange;
h) drying the monolith material at room temperature drying and at 80 C. under vacuum; and
i) further surface modifying with octadecyltrichlorosilane wherein any free silanol groups remaining from said surface modification are endcapped with chlorotrimethylsilane.
290. A porous inorganicorganic hybrid monolith material having a chromatographically-enhancing pore geometry and a formula SiO2C2H4(SiO1.5)20 25 wherein said hybrid material has been surface modified with octadecyltrichlorosilane and wherein any free silanol groups remaining from said surface modification procedure are endcapped with chlorotrimethylsilane and wherein said material contains a plurality of macropores sufficient to result in reduced backpressure at chromatographically-useful flow rates.
291. A porous inorganicorganic hybrid monolith material having a chromatographically-enhancing pore geometry and a formula SiO2C2H4(SiO1.5)20 25, produced by the process of
a) preparing an aqueous solution 1,2-bis(trimethoxysilyl)ethane and tetramethoxysilane in the presence of a 0.09 molar acetic acid solution and the surfactant Pluronic P-123 to produce a polyorganoalkoxysiloxane;
b) incubating said solution for 2 days at 45 C., resulting in a three-dimensional gel having a continuous, interconnected pore structure;
c) aging the gel in 1 molar ammonium hydroxide at 60 C. for 2 days to yield a solid monolith material;
d) rinsing the monolith material with water;
e) modifying the pore structure of said monolith material by hydrothermal treatment at 155 C. for 24 h in 0.1 M tris(hydroxymethyl)aminomethane, pH adjusted to 10.6;
f) rinsing the monolith material with water followed by a solvent exchange;
g) acid washing the monolith material in 1 molar hydrochloric acid for 24 hours at 98 C.;
h) rinsing the monolith material with water followed by a solvent exchange;
i) drying the monolith material at room temperature drying and at 80 C. under vacuum, and
j) further surface modifying with octadecyltrichlorosilane wherein any free silanol groups remaining from said surface modification are endcapped with chlorotrimethylsilane.
292. A porous inorganicorganic hybrid monolith material having a chromatographically-enhancing pore geometry and a formula SiO2HOC3H6SiO1 50 15 wherein said hybrid material has been surface modified with dodecylsiocyante and wherein said material contains a plurality of macropores sufficient to result in reduced backpressure at chromatographically-useful flow rates.
293. A porous inorganicorganic hybrid monolith material having a chromatographically-enhancing pore geometry and a formula SiO2HOC3H6SiO1.50 15, produced by the process of
a) preparing an aqueous solution methacryloxypropyltrimethoxysilane and tetramethoxysilane in the presence of a 0.015 molar acetic acid solution and the surfactant Triton X-100 or Triton 405 to produce a polyorganoalkoxysiloxane;
b) incubating said solution for 3 days at 45 C., resulting in a three-dimensional gel having a continuous, interconnected pore structure;
c) aging the gel in 1 molar ammonium hydroxide at 60 C. for 3 days to yield a solid monolith material;
d) rinsing the monolith material with water;
e) modifying the pore structure of said monolith material by hydrothermal treatment at 155 C. for 24 h in 0.1 M tris(hydroxymethyl)aminomethane, pH adjusted to 10.6;
f) rinsing the monolith material with water followed by a solvent exchange;
g) acid washing the monolith material in 1 molar hydrochloric acid for 24 hours at 98 C.;
h) rinsing the monolith material with water followed by a solvent exchange;
i) drying the monolith material at room temperature drying and at 80 C. under vacuum, and
j) further surface modifying with dodecylisocyanate.
The claims below are in addition to those above.
All refrences to claim(s) which appear below refer to the numbering after this setence.
1. A method programmed for execution in a computing environment for providing a digital image to a first website that supports a first resolution format of the digital image and a second website that supports a second resolution format of the digital image, the method comprising:
receiving from the digital image to be stored to the first website;
storing the digital image in the first resolution format to the first website and associating therewith a unique first type identifier;
connecting to the second website;
storing the second resolution format of the digital image to the second website and associating therewith a unique second type identifier; and
storing in a related manner said first and second unique type identifiers, wherein the first resolution format of the digital image is linked to the second resolution format of the digital image.
2. A method in accordance with claim 1, wherein the second resolution format of the digital image is provided by accessing the first website, further comprising:
receiving a request for a copy of the digital image on the first website;
determining the unique first type identifier of the digital image;
utilizing the related storage to obtain the second type identifier of the requested digital image; and
connecting to the second website and employing the second type identifier to obtain the second resolution format of the digital image.
3. A method in accordance with claim 1, further comprising:
manipulating the second resolution format of the digital image on said second website to make changes;
determining the unique second type identifier of the digital image;
utilizing the related storage to obtain the first type identifier of the digital image; and
connecting to the first website and employing the first type identifier to provide a first resolution format of the changed second resolution format of the digital image.
4. A method in accordance with claim 1, wherein the first resolution format is a low resolution digital image format and said second resolution format is a high resolution digital image format.
5. A method in accordance with claim 1, wherein the first website is a social network site and the second website is a photo service provider website.
6. A method in accordance with claim 1, wherein the unique first type identifier is provided by the first website.
7. A method in accordance with claim 1, wherein the unique first type identifier is provided by the first website and the unique second type identifier is provided by the second website.
8. A method in accordance with claim 1, wherein the storing of the first and second type identifiers in a related manner is provided in an Extensible Markup Language (XML) manifest.
9. A method in accordance with claim 8, wherein the XML manifest comprises rules for structure and content for the linking of the first resolution format of the digital image to the second resolution format of the digital image.
10. A method for execution in a computing environment for providing from a first website that supports a first resolution format of a digital image, a second resolution format of the digital image, the method comprising:
receiving from one of a plurality of users the digital image to be stored to the first website;
providing a unique first type identifier and storing the first resolution format of the digital image to the first website;
connecting to a second website, the second website providing support for the second resolution format;
providing a unique second type identifier and storing the second resolution format of the digital image to the second website;
storing in a related manner the first and second unique type identifiers, wherein the first resolution format of the digital image is linked to the second resolution format of the digital image;
receiving a request for a copy of the digital image on the first website;
determining the unique first type identifier of the digital image;
utilizing the related storage to obtain the second type identifier of the requested digital image; and
connecting to the second website and employing the second type identifier to obtain the second resolution format of the digital image.
11. A method in accordance with claim 10, wherein the first resolution format is a low resolution digital image format and the second resolution format is a high resolution digital image format.
12. A method in accordance with claim 10, wherein the first website is a social network site and the second website is a photo service provider website.
13. A method for execution in a computing environment for propagating updates of a first resolution of a digital image located on a first website to a second website having a second resolution of the digital image located thereon, the method comprising:
providing a unique first type identifier for the first resolution digital image;
providing a unique second type identifier for the second resolution digital image;
storing in a related manner the first and second unique type identifiers to thereby link the first resolution format of the digital image to the second resolution format of the digital image, wherein either resolution digital image may be identified given the other resolution digital image;
recognizing an update to the first resolution digital image, wherein the first resolution is a higher resolution format than the second resolution;
providing a second resolution format of said updated first resolution digital image; and
utilizing the related storage of the first and second unique type identifies to identify and replace the related second resolution digital image with the second resolution format of the updated first resolution digital image.
14. A method in accordance with claim 13, wherein the first resolution is a low resolution digital image format and the second resolution is a high resolution digital image format.
15. A method in accordance with claim 13, wherein the first website is a social network site and the second website is a photo service provider website.
16. A method in accordance with claim 13, wherein the update to the first resolution digital image is a cropping of the digital image.
17. A method in accordance with claim 13, wherein the update to the first resolution digital image comprises enhancements to the digital image.