Granted Patent
B2
US 12,202,806 · App. 17/248,924 · Granted Jan 21, 2025
Eco-friendly materials and methods for renewable and sustainable applications in material chemistry
Inventors:
Jayaraman Sivaguru (Fargo, ND); Akila Iyer (Fargo, ND); Mukund Sibi (Fargo, ND); Dean Webster (Fargo, ND); Saravana Kumar Rajendran (Fargo, ND); Ramya Raghunathan (Fargo, ND); Ravichandanath Singathi (Fargo, ND); Retheesh Krishnan (Fargo, ND); Anthony Clay (Fargo, ND)
Assignee:
NDSU RESEARCH FOUNDATION
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Abstract
The invention relates to novel hydrazide-based templates, methods of making the same, and methods of using the hydrazide-based templates as molecular scaffolds for asymmetric light driven transformations, light driven material synthesis, and biological applications. Furthermore, the present invention relates to photoinitiators, monomers, and polymers derived from biomass, together with methods and methods of using the same.
Claims (22)
1. A biomass derived, photodegradable polymer comprising:
at least one first monomeric unit derived from biomass, wherein the first monomeric unit is derived from lignin and comprises a methacrylate; and
at least one second monomeric unit derived from biomass comprising an arylmethyl, a benzoin, or a phenacyl phototrigger.
2. The photodegradable polymer of claim 1 , further comprising at least one third monomeric unit, wherein the third monomeric unit is not derived from biomass.
3. The photodegradable polymer of claim 1 , wherein the first monomeric unit is also a photoinitiator.
4. The photodegradable polymer of claim 1 , wherein photocleavage of said polymer occurs from exposure to light from about 300 nm to about 450 nm in wavelength.
5. The photodegradable polymer of claim 1 , wherein the second monomeric unit comprises a phenacyl phototrigger.
6. The photodegradable polymer of claim 1 , wherein the first monomeric unit is derived from vanillin, ortho-vanillin, or iso-vanillin.
7. The photodegradable polymer of claim 1 , wherein the first monomeric unit has the formula:
wherein A is H or Ome.
8. The photodegradable polymer of claim 1 , wherein the photodegradable polymer comprises a greater number of first monomeric units than second monomeric units.
9. The photodegradable polymer of claim 2 , wherein the photodegradable polymer comprises greater numbers of third monomeric units compared to the number of second monomeric units.
10. The photodegradable polymer of claim 1 , wherein photodegradable polymer comprises a plurality of second monomeric units that photocleave at different wavelengths.
11. The photodegradable polymer of claim 2 , wherein the third monomeric unit is obtained from a petroleum product or is chemically or enzymatically synthesized.
12. The photodegradable polymer of claim 2 , wherein the third monomeric unit is a hydrophilic monomer.
13. The photodegradable polymer of claim 2 , wherein the third monomeric unit comprises an alkylene glycol.
14. A method for recycling the photodegradable polymer of claim 1 , the method comprising:
exposing the photodegradable polymer to light having a wavelength selected so as to cause photocleavage of the polymer to yield one or more recycled monomers or oligomers.
15. The method of claim 14 , wherein the light is from about 300 nm to about 450 nm in wavelength.
16. The method of claim 14 , wherein the recycled monomer or oligomer has the formula:
wherein A is H or OMe.
17. The method of claim 14 , further comprising utilizing at least one of the recycled monomers or oligomers to synthesize a recycled polymer comprising the recycled monomer or oligomer.
Assignments (3)
CONFIRMATORY LICENSE
Recorded Nov 24, 2023
From: NORTH DAKOTA STATE UNIVERSITY
To: NATIONAL SCIENCE FOUNDATION
Reel/Frame 065675/0463 →
ASSIGNMENT OF ASSIGNOR'S INTEREST
Recorded Feb 25, 2021
From: SIVAGURU, JAYARAMAN; IYER, AKILA; SIBI, MUKUND; WEBSTER, DEAN; RAJENDRAN, SARAVANA KUMAR; RAGHUNATHAN, RAMYA; SINGATHI, RAVICHANDANATH; KRISHNAN, RETHEESH; CLAY, ANTHONY
To: NORTH DAKOTA STATE UNIVERSITY
Reel/Frame 055408/0799 →
ASSIGNMENT OF ASSIGNOR'S INTEREST
Recorded Feb 25, 2021
From: NORTH DAKOTA STATE UNIVERSITY
To: NDSU RESEARCH FOUNDATION
Reel/Frame 055409/0777 →
Continuity (6)
Continuation
PCTUS2017021277
· Mar 8, 2017
Provisional Application
62324189
· Apr 18, 2016
Provisional Application
62324194
· Apr 18, 2016
Provisional Application
62305044
· Mar 8, 2016
References Cited (85)
US 4530747A
· Donges
· 1985
[cited by examiner]
US 8835558B2
· Lee et al.
· 2014
[cited by applicant]
US 9738753B2
· Sivaguru
· 2017
[cited by examiner]
JP 2009203401A
· 2009
[cited by applicant]
WO 2012051448A1
· 2012
[cited by applicant]
Rajendran et al., Programmed Photodegradation of Polymeric/Oligomeric Materials Derived from Renewable Bioresources, Angewandte Chemie, 54, pp. 1159-1163, Published online: Nov. 12, 2014.
[cited by examiner]
Kurchan, Alexei N. et al., “Dithiane and Trithiane-based Photolabile Molecular Linkers Equipped with Amino-Functionality: Synthesis and Quantum Yields of Fragmentation”, Journal of Photochemistry and Photobiology A: Che…
[cited by applicant]
NDSU Research Foundation, “The International Search Report and Written Opinion of the International Searching Authority”, in connection to PCT/US17/21277 filed Mar. 8, 2017 mailed May 22, 2017.
[cited by applicant]
Abbas et al., “Original and efficient synthesis of 2:1-[α/aza]-oligomer precursors”, Tetrahedron Letters, vol. 50, pp. 4158-4160, 2009.
[cited by applicant]
Al-Sehemi, Abdullah, “Synthesis Characterization and Stereostructures of the Pyridazino[6, 1-b]Quinazolinones”, UKAU: Sci, vol. 18, pp. 47-62, 2006.
[cited by applicant]
Al-Sehemi et al., “Stereoisomerism in 3-[N-(2-acetoxypropanoyl)-N-acylamino]-quinazolin-4(3H)-ones, enantioselective acylating agents”, J. Chem. Soc., Perkin Trans. 1, pp. 4413-4421, 2000.
[cited by applicant]
Al-Sehemi et al., “3-Di-[(S)-2-acetoxypropanoyl]aminoquinazolin-4(3H)-ones: stereostructure and application in kinetic resolution of amines”, Tetrahedron Letters, vol. 41, pp. 2243-2246, 2000.
[cited by applicant]
Al-Sehemi et al., “3-(N,N-Diacylamino)quinazolin-4(3H)-ones as enantioselective acylating agents for amines”, Tetrahedron Letters, vol. 41, pp. 2239-2242, 2000.
[cited by applicant]
Anderson et al., “Concepts for ligand design in asymmetric catalysis: a study of chiral amino thiol ligands”, Tetrahedron: Asymmetry, vol. 9, pp. 3461-3490, 1998.
[cited by applicant]
Anderson et al., “A Photo-Induced Rearrangement Involving Aryl Participation”, Tetrahedron Letters, No. 1, pp. 1-4, 1962.
[cited by applicant]
Aoki et al., “N-Phenylation of N-Arylaminophthalimides with Triphenylbismuth and Cupric Acetate: A Convenient Synthesis of 1-Aryl-1-Phenylhydrazines”, Synthetic Communications, www.tandfonline.com/loi/lsyc20, 11 pages, …
[cited by applicant]
Arthur et al., “Stereostructural behavior of N-N atropisomers: Two conglomerate crystallisations and a crystallisation-induced deracemisation”, CrysEngComm, vol. 11, pp. 610-619, Dec. 9, 2008.
[cited by applicant]
Atkinson et al., “Resolution of N-Benzyl-N-(1,2-Dihydro-2-Oxoquinolin-1-YL)Glycine”, Tetrahedron Letters, No. 41, pp. 4001-4002, 1979.
[cited by applicant]
Atkinson et al., “Rotational Isomerism in N-(N-Heteroaryl)arenesulphenamides”, J. Chem. Soc. Perkin Trans. 2, pp. 1490-1495, Jan. 1, 1979.
[cited by applicant]
Atkinson et al., “The N—N Bond as a Chiral Axis: 3-(Diacylamino)quinazolin-4(3H)ones as Chiral Acylating Agents”, J. Chem. Soc., Chem. Commun., pp. 1159-1160, Jan. 1, 1994.
[cited by applicant]
Atkinson et al., “Completely diastereoselective aziridination of α,β-unsaturated acids via intramolecular reaction of 3-acetoxyaminoquinazolin-4(3H)-ones”, Tetrahedron Letters, vol. 43, pp. 2083-2085, 2002.
[cited by applicant]
Auvergne et al., “Biobased Thermosetting Epoxy: Present and Future”, Chem. Rev., vol. 114, pp. 1082-1115, 2014.
[cited by applicant]
Barsotti et al., “Photochemical processes induced by the irradiation of 4-hydroxybenzophenone in different solvents”, Photochem. Photobiol. Sci., vol. 14, pp. 2087-2096, 2015.
[cited by applicant]
Besson et al., “Conversion of Biomass into Chemicals over Metal Catalysts”, Chem. Rev., vol. 114, pp. 1827-1870, 2014.
[cited by applicant]
Bishop et al., “Torsional Barriers in NN′-Diacylhydrazines”, Chemical Communications, pp. 672-674, Jan. 1, 1967.
[cited by applicant]
Bourel et al., “Improved Synthesis of Pyridazinediones Under Microwave Irradiation”, Tetrahedron Letters, vol. 37, No. 24, pp. 4145-4148, 1996.
[cited by applicant]
Brosse et al., “A New Synthetic Route to Protected α-Hydrazinoesters in High Optical Purity Using the Mitsunobu Protocol”, J. Org. Chem., vol. 66, pp. 2869-2873, 2001.
[cited by applicant]
Chatani et al., “The power of light in polymer science: photochemical processes to manipulate polymer formation, structure, and properties”, Polym. Chem., vol. 5, pp. 2187-2201, 2014.
[cited by applicant]
Chan, Dominic, “Promotion of Reaction of N—H Bonds with Triarylbismuth and Cupric Acetate”, Tetrahedron Letters, vol. 37, No. 50, pp. 9013-9016, 1996.
[cited by applicant]
Conley et al., “A New Synthetic Route to Authentic N-Substituted Aminomaleimides”, J. Org. Chem., vol. 70, pp. 4553-4555, 2005.
[cited by applicant]
Coogan et al., “Synthesis of unsymmetrical 3,3′-biquinazoline-2,2′-diones by condensation of 3-aminoquinazolinones with benzoxazinones; fortuitous discovery, and further syntheses of 4-H-3-oxo-1,9a, 10-triazaanthracen-9…
[cited by applicant]
Coogan et al., “Tetraacyl hydrazines and 3,3′-biquinazoline-4,4′-diones; synthesis, studies of rotational barriers and deracemisation”, J. Chem. Soc., Perkin Trans. 2, pp. 2060-2066, 2000.
[cited by applicant]
D'Acquarica et al., “Dynamic HPLC on chiral stationary phases: A powerful tool for the investigation of stereomutation processes”, J. Sep. Sci., vol. 29, pp. 1508-1516, 2006.
[cited by applicant]
Draghici, Cristian, “Discovery of a Novel Ring Fragmentation Reaction; Efficient Preparation of Tethered Aldehyde Ynoates and N-Containing Heterocycles; Radical Addition Approach to Asymmetric Amine Synthesis”, A Disser…
[cited by applicant]
Fletcher et al., “Conformational Changes in Tetra-alkylhydrazines”, Chemical Communications, 706-708, Jan. 1, 1969.
[cited by applicant]
Gandini et al., “The Furan Counterpart of Poly(ethylene terephthalate): An Alternative Material Based on Renewable Resources”, Journal of Polymer Science: Part A: Polymer Chemistry, vol. 47, pp. 295-298, 2008.
[cited by applicant]
Givens et al., “Applications of p-hydroxyphenacyl (pHP) and coumarin-4-ylmethyl photoremovable protecting groups”, Photochem. Photobiol. Sci., vol. 11, pp. 472-488, 2012.
[cited by applicant]
Gomes et al., “Synthesis and Characterization of Poly(2,5-furan dicarboxylate)s Based on a Variety of Diols”, Journal of Polymer Science Part A: Polymer Chemistry, vol. 49, pp. 3759-3768, 2011.
[cited by applicant]
Guardado-Alvarez et al., “Nanovalve activation by surface-attached photoacids”, Chem. Commun. vol. 50, pp. 8388-8390, 2014.
[cited by applicant]
Harmsen et al., “Green building blocks for biobased plastics; biobased processes and market development”, Wageningen UR, 79 pages, Jan. 2013.
[cited by applicant]
Hynes, Jr et al., “N-Amination of Pyrrole and Indole Heterocycles with Monochloramine (NH2C1)”, J. Org. Chem., vol. 69, pp. 1368-1371, 2004.
[cited by applicant]
Iwata et al., “Photo-induced glycosylation using reusable organophotoacids”, Chem. Commun., vol. 50, pp. 10695-10698, 2014.
[cited by applicant]
Jin et al., “Alcohols as alkylating agents in heteroarene C—H functionalization”, Nature, vol. 525, pp. 87-90, Sep. 3, 2015.
[cited by applicant]
Kaminski et al., “Design, synthesis, and anticonvulsant activity of N-phenylamino derivatives of 3,3-dialkyl-pyrrolidine-2,5-diones and hexahydro-isoindole-1,3-diones”, Bioorganic & Medicinal Chemistry, vol. 16, pp. 492…
[cited by applicant]
Karton-Lifshin et al., ““Donor-Two-Acceptor” Dye Design: A Distinct Gateway to NIR Fluorescence”, J. Am. Chem. Soc., vol. 134, pp. 20412-20420, 2012.
[cited by applicant]
Keitz et al., “A Tandem Approach to Photoactivated Olefin Metathesis: Combining a Photoacid Generator with an Acid Activated Catalyst”, J. Am. Chem. Soc., vol. 131, pp. 2038-2039, 2009.
[cited by applicant]
Kim et al., “Use of N—N Bond Stereodynamics in Ring-Closing Metathesis to Form Medium-Sized Rings and Macrocycles”, Organic Letters, vol. 6, No. 23, pp. 4351-4353, 2004.
[cited by applicant]
Korsch et al., “Restricted Rotation About N—N Single Bonds, The Conformation of Tetrahydropyridazine Rings”, Tetrahedron Letters, No. 47, pp. 5897-5903, 1966.
[cited by applicant]
Kumasaka et al., “Photoexcited States of UV Absorbers, Benzophenone Derivatives”, Photochemistry and Photobiology, vol. 90, pp. 727-733, 2014.
[cited by applicant]
Lim et al., “Novel Route to Azobenzenes via Pd-Catalyzed Coupling Reactions of Ayl Hydrazides with Aryl Halides, Followed by Direct Oxidations”, Organic Letters, vol. 5, No. 7, pp. 979-982, 2002.
[cited by applicant]
Moreau et al., “Recent catalytic advances in the chemistry of substituted furans from carbohydrates and in the ensuing polymers”, Topics in Catalysis, vol. 27. Nos. 1-4, pp. 11-30, Feb. 2004.
[cited by applicant]
Moriarty et al., “Conformational Studies on the Amido Group, Hindered Internal Rotation in N,N1-Dialkyl Hydrazocarboxylates”, Tetrahedron Letters, No. 17, pp. 1603-1609, 1967.
[cited by applicant]
Ottersbach et al., “Induction of chirality: experimental evidence of atropisomerism in azapeptides”, Chem. Commun., vol. 48, pp. 5772-5774, 2012.
[cited by applicant]
Palit, Dipak, “Photophysics and excited state relaxation dynamics of p-hydroxy and p-amino-substituted benzophenones: a review” Res. Chem. Intermed., vol. 31, No. 1-3, pp. 205-225, 2005.
[cited by applicant]
Prasad Hari et al., “The Photoredox-Catalyzed Meerwein Addition Reaction: Intermolecular Amino-Arylation of Alkenes”, Angew. Chem. Int. Ed., vol. 53, pp. 725-728, 2014.
[cited by applicant]
Rajendran et al., “Programmed Photodegradation of Polymeric/Oligomeric Materials Derived from Renewable Bioresources”, Angew. Chem. Int. Ed., vol. 54, pp. 1159-1163, 2015.
[cited by applicant]
Reijenga et al., “Development of Methods for the Determination of pK
[cited by applicant]
Rosatella et al., “5-Hydroxymethylfurfural (HMF) as a building block platform: Biological properties, synthesis and synthetic applications”, Green Chem., vol. 13, pp. 754-793, 2011.
[cited by applicant]
Rosen et al., “Total Synthesis of Dixiamycin B by Electrochemical Oxidation”, J. Am. Chem. Soc., vol. 136, pp. 5571-5574, 2014.
[cited by applicant]
Schneider et al., “Effect of co-initiator ratio on the polymer properties of experimental resin composites formulated with camphorquinone and phenyl-propanedione”, Dental Materials, vol. 25, pp. 369-375, 2009.
[cited by applicant]
Shen et al., “Comparison of Electrophilic Amination Reagents for N-Amination of 2-Oxazolidinones and Application to Synthesis of Chiral Hydrazones”, J. Org. Chem. vol. 67, pp. 6236-6239, 2002.
[cited by applicant]
Shirai et al., “Photoacid and Photobase Generators: Prospects and Their use in the Development of Polymeric Photosensitive Systems”, Bull. Chem. Soc. Jpn., vol. 71, pp. 2483-2507, 1998.
[cited by applicant]
Simkovitch et al., “Comparison of the rate of excited-state proton transfer from photoacids to alcohols and water”, Journal of Photochemistry and Photobiology A: Chemistry, vol. 277, pp. 90-101, 2014.
[cited by applicant]
Sunal et al., “Monoamine oxidase inhibitory activities of novel 3,4-dihydroquinolin-(1H)-2-one derivatives”, J Neural Transm., vol. 114, pp. 717-719, 2007.
[cited by applicant]
Tehfe et al., “Photopolymerization Reactions: On the Way to a Green and Sustainable Chemistry”, Appl. Sci., vol. 3, pp. 490-514, 2013.
[cited by applicant]
Tolbert et al., “Photoexcited Proton Transfer from Enhanced Photoacids”, J. Am. Chem. Soc., vol. 116, pp. 10593-10600, 1994.
[cited by applicant]
Torti et al., “Aryl tosylates as non-ionic photoacid generators (PAGs): photochemistry and applications in cationic photopolymerizations”, RSC Adv., vol. 5, pp. 33239-33248, 2015.
[cited by applicant]
Trapp, Oliver, “Interconversion of Stereochemically Labile Enantiomers (Enantiomerization)”, Topics in Current Chemistry, vol. 341, pp. 231-269, 2013.
[cited by applicant]
Tšubrik et al., “Arylation of Diversely substituted hydrazines by tri- and pentavalent organobismuth reagents”, Tetrahedron, vol. 60, pp. 8363-8373, 2004.
[cited by applicant]
Van Putten et al., “Hydroxymethylfurfural, A Versatile Platform Chemical Made from Renewable Resources”, Chem. Rev., vol. 113, pp. 1499-1597, 2013.
[cited by applicant]
Verma et al., “Conformational Analysis about the Nitrogen-Nitrogen′ Bond by Nuclear Magnetic Resonance Spectroscopy. N′-Sulfonyl Derivatives of N-Aminocamphorimide”, J. Org. Chem., vol. 38, No. 21, pp. 3745-3749, 1973.
[cited by applicant]
Verma et al., “Conformational Analysis by Nuclear Magnetic Resonance Spectroscopy. N′Derivatives of N-Aminocamphorimides”, J. Org. Chem., vol. 38, No. 5, pp. 1004-1010, 1973.
[cited by applicant]
Verma et al., “Conformational Analysis About N—N Bond by NMR Spectroscopy:N′-Sulphonyl Derivatives of N-Aminoimides of Anthracene-Citraconic Anhydride and Naphthalene-Maleic Anhydride Adducts”, Bulletin of the Chemical …
[cited by applicant]
Verma et al., “Studies on N, N′-Diimidyl Systems by Nuclear Magnetic Resonance Spectroscopy”, Can J. Chem., vol. 52, pp. 2399-2402, 1974.
[cited by applicant]
Verma et al., “Structural Assignment by NMR Analyses of N-(Diacylamino)imide Derivatives. Diels-Alder Adducts of 2,3-Dimethylnaphthalene and 6,6-Diphenylfulvene with Maleic Anhydride”, Bulletin of the Chemical Society o…
[cited by applicant]
Verma et al., “Structural Assignment by NMR Spectroscopy: Restricted Rotation about Aryl C—N Bond and Configurations of Diels-Alder Adducts”, Bulletin of the Chemical Society of Japan, vol. 51. No. 2, pp. 520-523, 1978.
[cited by applicant]
Yang et al., “Synthesis and photopolymerization kinetics of benzophenone sesamol one-component photoinitiator”, Photochem Photobiol. Sci., vol. 12, pp. 323-329, 2013.
[cited by applicant]
Yao et al., “Controlled Polymerization of Next-Generation Renewable Monomers and Beyond”, Macromolecules, vol. 46, pp. 1689-1712, 2013.
[cited by applicant]
Sudha et al., “A convenient preparation of novel benzophenone derivatives”, J. Serb. Chem. Soc., vol. 73., No. 3, pp. 261-270, 2008.
[cited by applicant]
Il'Ichev et al., “Photochemical Reaction Mechanisms of 2-Nitrobenzyl Compounds: Methyl Ethers and Caged ATP”, J. Am. Chem. Soc., vol. 126, pp. 4581-4595, 2004.
[cited by applicant]
English Translation by WIPO of JP 2009-203401-A, 13 pages, (2009).
[cited by applicant]