Compositions, apparatus, systems, and methods for resolving electronic excited states
View Patent ↗The present disclosure relates, according to some embodiments, to molecules, including conjugated fused polycyclic molecules, that may receive excited state energy from other molecules (e.g., light-absorbing molecules) or directly from the irradiation sources. According to some embodiments, the disclosure relates to molecules, including conjugated fused polycyclic molecules, that may resolve (e.g., quench, dissipate) excited state energy, normally by way of releasing it as heat. (e.g., as heat). Conjugated fused polycyclic molecules of various structures are disclosed including Formula III: The disclosure further relates to methods of use and/or therapy using molecules of Formulas I, II, and/or III.
1. A composition comprising:
a photoactive molecule; and
a conjugated fused polycyclic molecule,
wherein the conjugated fused polycyclic molecule has a structure according to Formula II:
wherein
A 1 is independently carbonyl, C═C(R 13 )R 14 , O, S, S═O, S(O)═O, C═S,
R 13 is independently nitrile, C(O)OR 15 , C(O)R 16 , C(O)N(R 17 )R 18 , C(O)—S—R 19 , aryl, substituted or fused aryl,
R 14 is independently nitrile, C(O)OR 20 , C(O)R 21 , C(O)N(R 22 )R 23 , C(O)—S—R 24 , aryl, substituted or fused aryl,
R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 are each independently aryl, substituted aryl, fused aryl, alkyl, substituted alkyl, or branched alkyl,
A 2 is independently carbonyl, C═C(R 13 )R 14 , O, S, S═O, S(O)═O, C═S,
D 3 is independently H, hydroxyl, or R 25 ,
D 4 is independently H, hydroxyl, or R 26 , and
R 25 and R 26 are each independently alkyl, heteroalkyl, alkoxyl, heteroalkoxyl, aryl, heteroaryl, or fused aryl,
provided that
at least one of A 1 and A 2 is C═C(R 13 )R 14 ,
no more than one of R 13 and R 14 is aryl or substituted or fused aryl,
if neither A 1 nor A 2 is S, for each C═C(R 13 )R 14 , no more than one of R 13 and R 14 is nitrile, and
if neither A 1 nor A 2 is O, for each C═C(R 13 )R 14 , no more than one of R 13 and R 14 is C(O)OR 15/20 ,
wherein the conjugated fused polycyclic molecule is configured (a) to resolve at least one excited state of the photoactive molecule substantially without observable photochemical reaction, (b) to resolve at least one excited state of the photoactive molecule substantially non-radiatively, or (c) to resolve at least one excited state of the photoactive molecule substantially without observable photochemical reaction and substantially non-radiatively.
2. A composition according to claim 1 , wherein each R 13 and R 14 are different from each other.
3. A composition according to claim 1 , wherein D 3 and D 4 are hydrogen.
4. A composition according to claim 1 , wherein at least one of R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 is an alkyl group having from about 1 to about 30 carbon atoms.
5. A composition according to claim 1 , wherein one of R 13 and R 14 is nitrile.
6. A composition according to claim 1 , wherein neither R 13 nor R 14 is nitrile.
7. A composition according to claim 1 , wherein the conjugated fused polycyclic molecule comprises no more than 6 rings with no more than 4 of these rings fused to each other.
8. A composition according to claim 1 , wherein the photoactive molecule is selected from a pigment, a porphyrin, dibenzyolmethane, p-aminobenzoic acid, anthranilate, salicylate, cinnamic acid, dihydroxycinnamic acid, camphor, trihydroxycinnamic acid, dibenzalacetone naptholsulfonate, benzalacetophenone naphtholsulfonate, dihydroxy-naphthoic acid, o-hydroxydiphenyldisulfonate, p-hydroxdydiphenyldisulfonate, coumarin, respective salts thereof, respective derivatives thereof, and combinations thereof.
9. A composition according to claim 1 , wherein the photoactive molecule is selected from coumarin and derivatives thereof; diazole derivatives; quinine derivatives and salts thereof; quinoline derivatives; hydroxyl-substituted benzophenone derivatives; naphthalate derivatives; methoxy-substituted benzophenone derivatives; uric acid derivatives; vilouric acid derivatives; tannic acid and derivatives thereof; hydroquinone; benzophenone derivatives; 1,3,5-triazine derivatives; phenyldibenzimidazole tetrasulfonate and salts and derivatives thereof; terephthalyidene dicamphor sulfonic acid and salts and derivatives thereof; methylene bis-benzotriazolyl tetramethylbutylphenol and salts and derivatives thereof; bis-ethylhexyloxyphenol methoxyphenyl triazine and salts, diethylamino hydroxyl benzoyl and derivatives thereof; and combinations thereof.
10. A paint, a coating, a cosmetic, a sunscreen, a pharmaceutical preparation, a bituminous preparation, an ink, a toner, a photographic emulsion, a glass, or a fabric comprising a composition according to claim 1 .
11. A composition comprising:
a photoactive molecule; and
a conjugated fused polycyclic molecule,
wherein the conjugated fused polycyclic molecule has a structure according to Formula II:
wherein
A 1 is independently carbonyl, C═C(R 13 )R 14 , O, S, S═O, S(O)═O, C═S,
R 13 is independently nitrile, C(O)OR 15 , C(O)R 16 , C(O)N(R 17 )R 18 , C(O)—S—R 19 , aryl, substituted or fused aryl,
R 14 is independently nitrile, C(O)OR 20 , C(O)R 21 , C(O)N(R 22 )R 23 , C(O)—S—R 24 , aryl, substituted or fused aryl,
R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 are each independently aryl, substituted aryl, fused aryl, alkyl, substituted alkyl, or branched alkyl,
A 2 is independently carbonyl, C═C(R 13 )R 14 , O, S, S═O, S(O)═O, C═S,
D 3 is independently H, hydroxyl, or R 25 ,
D 4 is independently H, hydroxyl, or R 26 , and
R 25 and R 26 are each independently alkyl, heteroalkyl, alkoxyl, heteroalkoxyl, aryl, heteroaryl, or fused aryl,
provided that
at least one of A 1 and A 2 is C═C(R 13 )R 14 ,
each R 13 and R 14 are different from each other,
if neither A 1 nor A 2 is S, for each C═C(R 13 )R 14 , no more than one of R 13 and R 14 is nitrile, and
if neither A 1 nor A 2 is O, for each C═C(R 13 )R 14 , no more than one of R 13 and R 14 is C(O)OR 15/20 ,
wherein the conjugated fused polycyclic molecule is configured (a) to resolve at least one excited state of the photoactive molecule substantially without observable photochemical reaction, (b) to resolve at least one excited state of the photoactive molecule substantially non-radiatively, or (c) to resolve at least one excited state of the photoactive molecule substantially without observable photochemical reaction and substantially non-radiatively.
12. A composition according to claim 11 , wherein D 3 and D 4 are hydrogen.
13. A composition according to claim 11 , wherein at least one of R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 is an alkyl group having from about 1 to about 30 carbon atoms.
14. A composition according to claim 11 , wherein one of R 13 and R 14 is nitrile.
15. A composition according to claim 11 , wherein neither R 13 nor R 14 is nitrile.
16. A composition according to claim 11 , wherein the conjugated fused polycyclic molecule comprises no more than 6 rings with no more than 4 of these rings fused to each other.
17. A composition according to claim 11 , wherein the photoactive molecule is selected from a pigment, a porphyrin, dibenzyolmethane, p-aminobenzoic acid, anthranilate, salicylate, cinnamic acid, dihydroxycinnamic acid, camphor, trihydroxycinnamic acid, dibenzalacetone naptholsulfonate, benzalacetophenone naphtholsulfonate, dihydroxy-naphthoic acid, o-hydroxydiphenyldisulfonate, p-hydroxdydiphenyldisulfonate, coumarin, respective salts thereof, respective derivatives thereof, and combinations thereof.
18. A composition according to claim 11 , wherein the photoactive molecule is selected from coumarin and derivatives thereof; diazole derivatives; quinine derivatives and salts thereof; quinoline derivatives; hydroxyl-substituted benzophenone derivatives; naphthalate derivatives; methoxy-substituted benzophenone derivatives; uric acid derivatives; vilouric acid derivatives; tannic acid and derivatives thereof; hydroquinone; benzophenone derivatives; 1,3,5-triazine derivatives; phenyldibenzimidazole tetrasulfonate and salts and derivatives thereof; terephthalyidene dicamphor sulfonic acid and salts and derivatives thereof; methylene bis-benzotriazolyl tetramethylbutylphenol and salts and derivatives thereof; bis-ethylhexyloxyphenol methoxyphenyl triazine and salts, diethylamino hydroxyl benzoyl and derivatives thereof; and combinations thereof.
19. A paint, a coating, a cosmetic, a sunscreen, a pharmaceutical preparation, a bituminous preparation, an ink, a toner, a photographic emulsion, a glass, or a fabric comprising a composition according to claim 11 .
20. A method for resolving at least one excited energy state of a photoactive molecule, the method comprising:
positioning the photoactive molecule in electrical communication with a conjugated fused polycyclic molecule prior to, during, or following excitation of the photoactive molecule to the at least one excited energy state,
wherein the conjugated fused polycyclic molecule has a structure according to Formula II:
wherein
A 1 is independently carbonyl, C═C(R 13 )R 14 , O, S, S═O, S(O)═O, C═S,
R 13 is independently nitrile, C(O)OR 15 , C(O)R 16 , C(O)N(R 17 )R 18 , C(O)—S—R 19 , aryl, substituted or fused aryl,
R 14 is independently nitrile, C(O)OR 20 , C(O)R 21 , C(O)N(R 22 )R 23 , C(O)—S—R 24 , aryl, substituted or fused aryl,
R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 are each independently aryl, substituted aryl, fused aryl, alkyl, substituted alkyl, or branched alkyl,
A 2 is independently carbonyl, C═C(R 13 )R 14 , O, S, S═O, S(O)═O, C═S,
D 3 is independently H, hydroxyl, or R 25 ,
D 4 is independently H, hydroxyl, or R 26 , and
R 25 and R 26 are each independently alkyl, heteroalkyl, alkoxyl, heteroalkoxyl, aryl, heteroaryl, or fused aryl,
provided that
at least one of A 1 and A 2 is C═C(R 13 )R 14 ,
no more than one of R 13 and R 14 is aryl or substituted or fused aryl,
if neither A 1 nor A 2 is S, for each C═C(R 13 )R 14 , no more than one of R 13 and R 14 is nitrile, and
if neither A 1 nor A 2 is O, for each C═C(R 13 )R 14 , no more than one of R 13 and R 14 is C(O)OR 15/20 .
21. A method according to claim 20 , wherein the at least one excited state of the photoactive molecule is resolved substantially without observable photochemical reaction or without observable photosensitization reactions.
22. A method according to claim 20 , wherein the at least one excited state of the photoactive molecule is resolved substantially non-radiatively.
23. A method according to claim 20 , wherein the at least one excited state of the photoactive molecule is resolved substantially non-radiatively, substantially without observable photochemical reaction, and substantially without observable photosensitization reactions.