Stimuli-switchable moieties, monomers and polymers incorporating stimuli-switchable moieties, and methods of making and using same

Patent metadata

Field	Value
Publication number	US-2017267689-A1
Application number	US-201515506695-A
Country	US
Kind code	A1
Filing date	Aug 25, 2015
Priority date	Aug 25, 2014
Publication date	Sep 21, 2017
Grant date	—

Abstract

Stimuli-switchable moieties, monomers incorporating stimuli-switchable moieties, and polymers incorporating such stimuli-switchable moieties are provided. The stimuli-switchable moiety can be a pyrano aryl chromenone-derivative. The stimuli-switchable monomer can be a lactone monomer. The stimuli-switchable monomer can be an amino acid, which can be incorporated into a specific peptide sequence by peptide synthesis.

First claim

1 . A polymer comprising a plurality of monomeric units selected from the group consisting of pyranonaphtha chromenone derivatives, perylene chromenone deriviatives and lactone derivatives, wherein at least two of the monomeric units comprise a reversible stimuli-switchable moiety, wherein the polymer is reversibly switchable in response to an external stimuli, wherein the stimuli-switchable moiety undergoes structural isomerization upon exposure to the external stimuli, and wherein the external stimuli comprises light, heat, or chemical stimulus, and wherein the chemical stimulus optionally comprises a change in pH.

2 . The polymer as defined in claim 1 , wherein the polymer is switchable between a hydrophobic state and a hydrophilic state in response to the external stimuli, or is switchable between a hydrophilic state and a hydrophobic state in response to the external stimuli; and/or wherein the polymer is switchable between a colorless state and a colored state in response to the external stimuli, or is switchable between a colored state and a colorless state in response to the external stimuli.

3 . The polymer as defined in claim 1 , wherein the stimuli-switchable moiety comprises a pyranonaphtha chromenone derivative or a pyranoperylene chromenone having the structure (I) or (II):

4 . The polymer as defined in claim 3 , wherein the stimuli-switchable moiety reversibly switches from hydrophobic to hydrophilic, upon exposure to light having a wavelength in the range of approximately 250 nm to 450 nm or approximately 650 nm to 800 nm.

5 . The polymer as defined in claim 4 , wherein the stimuli-switchable moiety reversibly switches from hydrophilic to hydrophobic, upon an increase in temperature to above approximately 50° C.

6 . The polymer as defined in claim 4 , wherein a degree of change in a contact angle of the polymer is at least 1.5 times greater than a degree of change in a contact angle of a corresponding polymer incorporating a nitrobenzene-derived stimuli-switchable moiety.

7 . The polymer as defined in claim 1 , wherein the monomeric units comprise lactone derivatives, and wherein the stimuli-switchable moiety comprises a spiropyran, a spirooxazine, an azobenzene, a bisthienylethene, a flugide, 2-diazo-1,2-napthoquinone-5-sulfonyl-methylacrylamide, or a pyrano aryl chromenone derivative, which is optionally a pyranobenzyl chromenone derivative, a pyranonaphtha chromenone derivative, or a pyranoperylene chromenone.

8 . The polymer as defined in claim 1 , wherein the monomeric units comprise lactone derivatives, and wherein:
the stimuli-switchable moiety comprises a pyrano aryl chromenone derivative, optionally a pyranobenzyl chromenone derivative, a pyranonaphtha chromenone derivative, or a pyranoperylene chromenone, and the stimuli comprises light having a wavelength in the range of about 250 nm to about 450 nm, or in the range of about 650 nm and 800 nm; or the stimuli-switchable moiety comprises a spiropyran derivative, and the stimuli comprises light having a wavelength in the range of about 350 nm to about 550 nm.

9 . (canceled)

10 . (canceled)

11 . (canceled)

12 . The polymer as defined in claim 1 , wherein the polymer is reversibly switchable between the hydrophilic and hydrophilic states.

13 . The polymer as defined in claim 1 , wherein the stimuli is selected from the group consisting of light and heat.

14 . The polymer as defined in claim 1 , wherein the stimuli-switchable moiety is a photochromic moiety.

15 . The polymer as defined in claim 1 , wherein the polymer is tethered to a solid surface.

16 . The polymer as defined in claim 15 , wherein the surface is selected from the group consisting of a microfluidic chip, a display device, a selective size separator, a transducer, a nanoparticle, and a membrane.

17 . The polymer as defined in claim 15 , wherein the surface is biocompatible.

18 . (canceled)

19 . (canceled)

20 . (canceled)

21 . (canceled)

22 . (canceled)

23 . (canceled)

24 . A molecule comprising a stimuli-switchable moiety based on pyranonaphtha chromenone or pyranoperylene chromenone.

25 . The molecule as defined in claim 24 , wherein the stimuli-switchable moiety comprises the chemical structure (I) or (II):

wherein X denotes a remaining portion of the molecule.

26 . The molecule as defined in claim 25 , wherein the stimuli-switchable moiety reversibly switches from hydrophobic to hydrophilic, upon exposure to light having a wavelength in the range of 250 nm to 450 nm or approximately 650 nm to 800 nm.

27 . The molecule as defined in claim 25 , wherein the stimuli-switchable moiety reversibly switches from hydrophilic to hydrophobic, upon an increase in temperature to above approximately 50° C.

28 . The molecule as defined in claim 25 , wherein the molecule comprises a monomer for synthesizing a polymer, wherein X comprises one of the following groups:

29 . A polymerizable monomer having a reversible stimuli-switchable moiety, the monomer comprising a lactone, wherein the stimuli-switchable moiety is switchable in response to an external stimulus comprising light, heat, or chemical stimulus, wherein the chemical stimulus optionally comprises a change in pH, and wherein the stimuli-switchable moiety undergoes structural isomerization upon exposure to the external stimulus.

30 .- 45 . (canceled)

46 . A polymer as defined in claim 1 , wherein the structural isomerization comprises cis-trans isomerization, trans-cis isomerization, ring-closing, or ring-opening.

Assignees

• Univ Alberta

Inventors

• Montemagno Carlo David
• Abraham Sinoj
• Kumaran Surjith Kumar

Classifications

• C08G63/08

  Lactones or lactides · CPC title

• C09K2211/1088

  containing oxygen as the only heteroatom · CPC title

• C09K2211/145

  containing oxygen as the only heteroatom · CPC title

• C09K2211/1466

  containing nitrogen as the only heteroatom · CPC title

• C08G69/00

  Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule (products obtained from isocyanates or isothiocyanates C08G18/00; polyamide-imides C08G73/14) · CPC title