Solid support with a grafted chain
View Patent ↗Articles that contain a solid support with a grafted chain extending from the solid support, methods of making these articles, and various uses of the articles are described. More specifically, the grafted chain has a functional group that can react with or interact with target compound. Alternatively, the functional group on the grafted chain can react with a modifying agent to provide another group that can react with or interact with the target compound. The grafted chains are attached to the solid support through a ring-opened azlactone group. The articles can be used to purify the target compound or to separate the target compound from other molecules in a sample.
1. A method for preparing an article, the method comprising providing an azlactone-functionalized support of Formula (I)
wherein
SS comprises a solid support;
p is an integer equal to 0 or 1; and
each R 1 is independently selected from alkyl, heteroalkyl, aryl, or aralkyl;
forming a (meth)acryloyl-functionalized support of Formula (II)
SS—(CO)—NH—C(R 1 ) 2 —(CH 2 ) p —(CO)-Q-Y 1 -Q-(CO)—CR 2 ═CH 2 (II)
from the azlactone-functionalized support of Formula (I)
wherein
each group Q is independently a divalent group selected from oxy, thio, or —NR 3 — where R 3 is a hydrogen, alkyl, heteroalkyl, aryl, or aralkyl;
Y 1 is a first linking group comprising an alkylene, heteroalkylene, arylene, or combination thereof; and
R 2 is hydrogen or an alkyl;
polymerizing the (meth)acryloyl-functional support of Formula (II) with a monomer composition that comprises a monomer of Formula (III)
Z 1 —Y 2 —CR 2 ═CH 2 (III)
to form a grafted support of Formula (IV)
SS—(CO)—NH—C(R 1 ) 2 —(CH 2 ) p —(CO)-Q-Y 1 -Q-(CO)—CR 2 U 2 —CH 2 —U 1 (IV)
wherein
U 1 comprises at least one divalent monomeric unit of formula —CR 2 (Y 2 Z 1 )—CH 2 —;
U 2 is hydrogen or comprises at least one divalent monomeric unit of formula —CR 2 (Y 2 Z 1 )—CH 2 —;
Z 1 is a functional group selected from (1) an acidic group or a salt thereof, (2) an amino group or a salt thereof, (3) a hydroxyl group, (4) an azlactone group or a precursor of the azlactone group, (5) a glycidyl group, or (6) a combination thereof; and
Y 2 is a second linking group selected from a single bond or a divalent group comprising an alkylene, heteroalkylene, arylene, or combination thereof.
2. The method of claim 1 , wherein forming the (meth)acryloyl-functionalized support of Formula (II) comprises reacting the azlactone group of the azlactone-functionalized support of Formula (I) with a compound of Formula (IV)
HQ-Y 1 -Q-(CO)—CR 2 ═CH 2 (VI).
3. The method of claim 1 , wherein forming the (meth)acryloyl-functionalized support of Formula (II) comprises forming an intermediate of Formula (VIII)
SS—(CO)—NH—C(R 1 ) 2 —(CH 2 ) p —(CO)-Q-Y 1a -QH (VIII)
wherein
Y 1a comprises an alkylene, heteroalkylene, arylene, or combination thereof.
4. The method of claim 3 , further comprising reacting the intermediate of Formula (VIII) with a second compound having a first group capable that reacts with a nucleophilic group (-QH) and a second group that comprises an ethylenically unsaturated group.
5. The method of claim 1 , wherein the monomer of Formula (III) is of Formula (IIIa)
Z 1 —Y 2a -Q-(CO)—CR 2 ═CH 2 (IIIa)
wherein
Y 2a is a divalent group comprising an alkylene, heteroalkylene, arylene, or combination thereof.
6. An article comprising a grafted support of Formula (IV)
SS—(CO)—NH—C(R 1 ) 2 —(CH 2 ) p —(CO)-Q-Y 1 -Q-(CO)—CR 2 U 2 —CH 2 —U 1 (IV)
wherein
SS comprises a solid support;
p is an integer equal to 0 or 1;
each R 1 is each independently selected from alkyl, heteroalkyl, aryl, or aralkyl;
each Q is independently a divalent group selected from oxy, thio, or —NR 3 — where
R 3 is hydrogen, alkyl, heteroalkyl, aryl, or aralkyl;
Y 1 is a first linking group that comprises an alkylene, heteroalkylene, arylene, or combination thereof;
each R 2 is independently hydrogen or an alkyl;
U 1 comprises at least one divalent monomeric unit of formula —CR 2 (Y 2 Z 1 )—CH 2 —;
U 2 is hydrogen or comprises at least one divalent monomeric unit of formula —CR 2 (Y 2 Z 1 )—CH 2 —;
Y 2 is a second linking group selected from a single bond or a divalent group comprising an alkylene, heteroalkylene, arylene, or combination thereof; and
Z 1 is a functional group selected from (1) an acidic group or a salt thereof, (2) an amino group or a salt thereof, (3) a hydroxyl group, (4) an azlactone group or a precursor of the azlactone group, (5) a glycidyl group, or (6) a combination thereof.
7. The article of claim 6 , wherein the solid support is in the form of a bead.
8. The article of claim 6 , wherein the solid support comprises a crosslinked polymeric material.
9. A method for preparing an article, the method comprising providing an azlactone-functionalized support of Formula (I)
wherein
SS comprises a solid support;
p is an integer equal to 0 or 1; and
each R 1 is independently selected from alkyl, heteroalkyl, aryl, or aralkyl;
forming a (meth)acryloyl-functionalized support of Formula (II)
SS—(CO)—NH—C(R 1 ) 2 —(CH 2 ) p —(CO)-Q-Y 1 -Q-(CO)—CR 2 ═CH 2 (II)
from the azlactone-functionalized support of Formula (I)
wherein
each group Q is independently a divalent group selected from oxy, thio, or —NR 3 — where R 3 is a hydrogen, alkyl, heteroalkyl, aryl, or aralkyl;
Y 1 is a first linking group comprising an alkylene, heteroalkylene, arylene, or combination thereof; and
R 2 is hydrogen or an alkyl;
polymerizing the (meth)acryloyl-functional support of Formula (II) with a monomer composition that comprises a monomer of Formula (III)
Z 1 —Y 2 —CR 2 ═CH 2 (III)
to form a grafted support of Formula (IV)
SS—(CO)—NH—C(R 1 ) 2 —(CH 2 ) p —(CO)-Q-Y 1 -Q-(CO)—CR 2 U 2 —CH 2 —U 1 (IV)
wherein
U 1 comprises at least one divalent monomeric unit of formula —CR 2 (Y 2 Z 1 )—CH 2 —;
U 2 is hydrogen or comprises at least one divalent monomeric unit of formula —CR 2 (Y 2 Z 1 )—CH 2 —;
Z 1 is a functional group selected from (1) an acidic group or a salt thereof, (2) an amino group or a salt thereof, (3) a hydroxyl group, (4) an azlactone group or a precursor of the azlactone group, (5) a glycidyl group, or (6) a combination thereof; and
Y 2 is a second linking group selected from a single bond or a divalent group comprising an alkylene, heteroalkylene, arylene, or combination thereof; and
reacting the functional group Z 1 of the grafted support with a modifying agent of formula A-T to form a modified grafted support of Formula (V)
SS—(CO)—NH—C(R 1 ) 2 —(CH 2 ) p —(CO)-Q-Y 1 -Q-(CO)—CR 2 U 4 —CH 2 —U 3 (V)
wherein
U 3 includes at least one divalent monomeric unit of formula —CR 2 (Y 2 L-T)-CH 2 —;
U 4 is hydrogen or comprises at least one divalent monomeric unit of formula —CR 2 (Y 2 L-T)-CH 2 —;
L is a attachment group formed by reacting group Z 1 with a modifying group A of the modifying agent; and
T is a remainder of the modifying agent A-T and is equal to the modifying agent A-T minus the modifying group A.
10. The method of claim 9 , wherein the modifying agent is an affinity ligand comprising at least one nucleophilic group.
11. The method of claim 9 , wherein the modifying agent comprises a first group that is a nucleophilic and a second group that is basic, acidic, or a salt thereof.
12. The method of claim 9 , wherein the modifying agent comprises a first group that is nucleophilic and a second group that is hydrophobic.
13. The method of claim 9 , wherein the modifying agent comprising a first group that is nucleophilic and a second group that is metal-chelating.
14. The method of claim 9 , wherein the modifying agent is a biomolecule.