Polymerizable gemini dicarboxlate surfactants and lyotropic liquid crystals and membranes made therefrom
AssigneeWisconsin Alumni Research Foundation
InventorsMahesh Kalyana Mahanthappa, Gregory Paul Sorenson
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Abstract
The disclosure provides anionic Gemini surfactants comprising at least two carbonyl moieties and at least two aliphatic moieties. In some aspects, at least two of the aliphatic moieties comprise at least seven carbon atoms and at least one pair of conjugated carbon-to-carbon double bonds. The anionic Gemini surfactants are polymerizable and may be used to prepare triply periodic multiply continuous lyotropic phase and polymers thereof that substantially retain triply periodic multiply continuous lyotropic phase structure.
Claims28
A polymerizable anionic Gemini surfactant having the following structure:
- wherein X1 and X2 are each independently an optionally substituted branched, unbranched, or cyclic aliphatic groups having from four to 30 carbon atoms;
- Z1 and Z2 are integers, each independently having a value of zero, one, two, or three;
- Y is a covalently bound divalent linker;
- M1 and M2 are the same or different and are each independently selected from hydrogen, hydroxyl, —O(C1-C8 alkyl)N(CH3)3+(X−) where X− is a counterion, —(C0-C8 alkyl)NR11R12, —O(C1-C8 alkyl)NR11R12, —NH(C1-C8 alkyl)NR11R12, —NH(CH—R13)COOH, —OR11, —NR11R14, and —O−(M+) where M+ is a counterion, wherein R11, R12, and R14 are independently chosen from hydrogen and optionally substituted C1-C8 alkyl, and wherein R13 is an amino acid side chain;
- and
- R1 through R10 are each independently chosen from hydrogen, fluoride, chloride, bromide, C1-C8 alkyl, C2-C8 alkenyl, tri(C1-C4 alkyl)silyl, and substituted or unsubstituted phenyl.
A method of preparing a polymerizable Gemini surfactant comprising:
- (a) contacting a carboxylic acid, a carboxylate salt, or a carboxylate ester with a quantity of a base to thereby deprotonate the alpha carbon of the carboxylic acid, carboxylate salt, or carboxylate ester, wherein the carboxylic acid, carboxylate salt, or carboxylate ester comprises at least seven carbon atoms and at least one carbon-to-carbon double bond;
- and
- (b) contacting the alpha carbon-deprotonated carboxylic acid, carboxylate salt, or carboxylate ester of (a) with a compound having the structure:
- wherein L1 and L2 comprise leaving groups and Y comprises a covalently bound divalent linker, whereby said contacting forms the Gemini surfactant.
A method of preparing a Gemini surfactant comprising a terminal diene of the formula
- the method comprising:
- contacting a Gemini dicarboxylate compound of Structure IV
- with an oxidizing agent to thereby prepare a Gemini dialdehyde of Structure V
- and
- contacting the Gemini dialdehyde with a (1-trialkylsilyl)allyl-3-boronic acid or an ester thereof, which contact is followed by a silanol elimination reaction with an acid or a base to thereby prepare the Gemini surfactant comprising the terminal diene;
- wherein X1 and X2 are each independently an optionally substituted branched, unbranched, or cyclic aliphatic group having from four to 30 carbon atoms;
- Y is a covalently bound divalent linker;
- M1 and M2 are the same or different and are each independently selected from hydrogen, hydroxyl, —O(C1-C8 alkyl)N(CH3)3+(X−) where X− is a counterion, —(C0-C8 alkyl)NR11R12, —O(C1-C8 alkyl)NR11R12, —NH(C1-C8 alkyl)NR11R12, —NH(CH—R13)COOH, —NR11R14, and —O−(M+) where M+ is a counterion, wherein R11, R12, and R14 are independently chosen from hydrogen and optionally substituted C1-C8 alkyl, and wherein R13 is an amino acid side chain;
- and
- R17 through R22 are each independently hydrogen, fluoride, chloride, bromide, C1-C8alkyl, C2-C8 alkenyl, tri(C1-C4 alkyl)silyl, and substituted or unsubstituted phenyl.
Dependencies are inferred from the claim text.